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No description available.

Indiana University-Purdue University Indianapolis (IUPUI) / The Ordovician (485-444 Ma) was a highly dynamic period, characterized by significant evolutionary and climatic change. Paleozoic fauna which evolved during the Great Ordovician Biodiversification Event (GOBE) populated extensive epicontinental seaways. Major sea level fluctuations during The Hirnantian glaciation are believed to have led to a mass extinction event at the End Ordovician. However, a reassessment of Early Paleozoic fossil assemblages suggests the onset of extinctions began in the mid-Katian, ~3 million years before the Hirnantian. The Kope formation, within the North American succession of the Katian, was deposited during the peak biodiversification of the GOBE at the point which a biological crisis begins. The well-studied series of interbedded shale and fossiliferous limestone beds, deposited within a shallow epeiric sea, provide ideal sedimentological and paleontological context to interpret sediment geochemistry recorded at the onset of a global mass extinction. For a high-resolution section of the Kope, δ34Spyrite show an extraordinary range of variability, up to 64.5‰, with systematic oscillations throughout the core. The isotope signal represents a mix of pyrite formed at the time of deposition and during diagenesis. As sea levels fluctuated, the amount of sediment delivery influenced the connection of sediment porewaters to overlying seawater sulfate and the location of the sulfate reduction zone, which in turn, masked the primary signal. Reactive iron data suggest low oxygen concentrations in the water column, however fossil assemblages found throughout the Kope suggest otherwise. Changes in sedimentation can mask the water column signal, so these data also capture an aggregate signal. δ15Nbulk show an upsection decrease of 4.4‰, followed by a 3.4‰ increase. Though this excursion can be interpreted as a switch to increased denitrification in a low oxygen environment, the fossil record suggests the data capture localized diagenetic reactions that occur below an oxic water column. Perturbations in the ocean-climate system is often based on the interpretation of stable isotope excursions, and although excursions are diagnostic of changes to biogeochemical cycles, they may not fully account for diagenetic reactions that mask primary signals. The results from the Kope demonstrate strong localized, not global, controls on the sediment geochemistry.

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.

Underlying all applications of sulfur isotope analyses is our understanding of isotope systematics. This dissertation tests some fundamental assumptions and assertions, drawn from equilibrium theory and a diverse body of empirical work on biochemical kinetics, as applied to the multiple sulfur isotope systematics of microbial sulfate reduction. I take a reductionist approach, both in the questions addressed and experimental approaches employed. This allows for a mechanistic, physically consistent interpretation of geological and biological sulfur isotope records. The goal of my work here is to allow interpreters a more biologically, chemically and physically parsimonious framework to decipher the signals coded in modern and ancient sulfur isotope records. / Earth and Planetary Sciences

The Kiruna mining district, located in the northern Norrbotten ore province, Sweden, is a geologically and economically important area, being the type-locality for Kiruna iron oxide-apatite (IOA) deposits and also host to a variety of other deposits including syngenetic stratiform exhalative Cu-(Fe-Zn) (Viscaria, Eastern Pahtohavare), epigenetic stratabound Cu ± Au (Pahtohavare), and iron oxide-copper-gold (IOCG, Rakkurijärvi) deposits. However, the timing of IOA versus IOCG within the tectonic evolution is in question based on structural investigations showing Cu- and Fe-sulfides occur in late-orogenic structures. Here we use an established tectonic framework to constrain mineral systems (tectonic/thermal drives, metal and ligand sources, fluid pathways, traps, remobilization mechanisms) related to the early and late phases of the Svecokarelian orogeny in the Kiruna mining district. U-Pb zircon geochronology of intrusions in the district indicates a thermal drive was present during the early phase of the Svecokarelian orogeny from ca. 1920-1865 Ma, however remains enigmatic for the late Svecokarelian orogeny. Zircon grains from a magnetite-ilmenite gabbro yielded an age of 1881 ± 8 Ma, coeval with the Kiirunavaara IOA deposit and suggested to represent an important generation of mafic magmatism related to the ore. Lithogeochemistry of early bimodal Svecokarelian intrusions in the district indicates a within-plate to active continental margin environment with a volcanic arc affinity, pointing to a back arc environment. Epsilon Ndi and 87Sr/86Sri values calculated from the U-Pb ages for the igneous intrusions were compared to samples of ore-related alteration from epigenetic Pahtohavare and Rakkurijärvi deposits, district greenstone, and Archean samples. Results show that each deposit sourced Sr and Nd from a variety of rocks suggesting broad fluid transport. Each deposit has a distinct Sr mixing trend suggesting they formed from different ore-forming fluids and pathways. This is supported by new structural data that constrain the folding event and the ore-related quartz-carbonate-sulfide veins in the Pahtohavare area to a late orogenic timing, compared to the early orogenic timing of Rakkurijärvi. Sulfide trace element and sulfur isotope data from structurally constrained ores within the tectonic framework also record distinct characteristics between early and late deposits. However, remobilization of early Pahtohavare sulfides associated to an increase in Co content and heavier sulfur isotope compositions is recorded. The results of this study illustrate that using a structural framework approach to constrain the ingredients of mineral systems is a powerful strategy for interpreting ore deposit processes in tectonically complex terrains where both IOA and IOCG deposits occur.

This thesis study is concerned with the genetic investigation of two epithermal gold deposits (Madendag and Kartaldag) in &Ccedil / anakkale, NW Turkey. The methodology comprises field and integrated laboratory studies including mineralogic-petrographic, geochemical, isotopic, and fluid inclusion analysis. Kartaldag deposit, hosted by dacite porphyry, is a typical vein deposit associated with four main alteration types: i) propylitic, ii) quartz-kaolin, iii) quartz-alunitepyrophyllite, iv) silicification, the latter being characterized by two distinct quartz generations as early (vuggy) and late (banded, colloform). Primary sulfide minerals are pyrite, covellite and sphalerite. Oxygen and sulfur isotope analyses, performed on quartz (&delta / 18O: 7.93- 8.95 &permil / ) and pyrite (&delta / 34S: -4.8 &permil / ) separates, suggest a magmatic source for the fluid. Microthermometric analysis performed on quartz yield a temperature range of 250-285 &ordm / C, and 0-1.7 wt % NaCl eqv. salinity. Madendag deposit, hosted by micaschists, is also vein type associated with two main alteration types: illite and kaolin dominated argillization and silicification, characterized by two distinct quartz phases as early and late. Oxygen isotope analyses on quartz (&delta / 18O: 9.55-18.19 &permil / ) indicate contribution from a metamorphic source. Microthermometric analysis on quartz yield a temperature range of 235-255 &ordm / C and 0.0-0.7 wt % NaCl eqv. salinity. The presence of alunite, pyrophyllite and kaolinite, vuggy quartz and covellite suggest a high-sulfidation epithermal system for Kartaldag. On the other hand, Madendag is identified as a low- sulfidation type owing to the presence of neutral pH clays and typical low temperature textures (e.g. colloform, comb, banded quartz).

No description available.

[Formulae and special characters can only be approximated here. Please see the pdf version of the abstract for an accurate reproduction.] The formation of world-class Archean orogenic gold deposits in the Eastern Goldfields Province of Western Australia was the result of a critical combination of physical and chemical processes that modified a single and widespread ore-fluid along fluid pathways and at the sites of gold deposition. Increased gold endowment in these deposits is associated with efficient regional-scale fluid focusing mechanisms and the influence of multiple ore-depositional processes at the deposit-scale. Measurement of the complexity of geologic features, as displayed in high-quality geologic maps of uniform data density, can be used to highlight areas that influence regional-scale hydrothermal fluid flow. Useful measurements of geological complexity include fractal dimensions of map patterns, density and orientation of faults and lithologic contacts, and proportions of rock types. Fractal dimensions of map patterns of lithologic contacts and faults highlight complexity gradients. Steep complexity gradients, between domains of high and low fractal dimensions within a greenstone belt, correspond to district-scale regions that have the potential to focus the flow of large volumes of hydrothermal fluid, which is critical for the formation of significant orogenic gold mineralization. Steep complexity gradients commonly occur in greenstone belts where thick sedimentary units overly more complex patterns of lithologic contacts, associated with mafic intrusive and mafic volcanic units. The sedimentary units in these areas potentially acted as seals to the hydrothermal Mineral Systems, which resulted in fluid-pressure gradients and increased fluid flow. The largest gold deposits in the Kalgoorlie Terrane and the Laverton Tectonic Zone occur at steep complexity gradients adjacent to thick sedimentary units, indicating the significance of these structural settings to gold endowment. Complexity gradients, as displayed in surface map patterns, are an indication of three-dimensional connectivity along fluid pathways, between fluid source areas and deposit locations. Systematic changes in the orientation of crustal-scale shear zones are also significant and measurable map features. The largest gold deposits along the Bardoc Tectonic Zone and Boulder-Lefroy Shear Zone, in the Eastern Goldfields Province, occur where there are counter-clockwise changes in shear zone orientation, compared to the average orientation of the shear zone along its entire length. Sinistral movement along these shear zones resulted in the formation of district-scale dilational jogs and focused hydrothermal fluid-flow at the Golden Mile, New Celebration and Victory-Defiance deposits. Faults and lithologic contacts are the dominant fluid pathways in orogenic gold Mineral Systems, and measurements of the density of faults and contacts are also a method of quantifying the complexity of geologic map patterns on high-quality maps. Significantly higher densities of pathways in areas surrounding larger gold deposits are measurable within 20- and 5-kilometer search radii around them. Large variations in the sulfur isotopic composition of ore-related pyrites in orogenic gold deposits in the Eastern Goldfields Province are the result of different golddepositional mechanisms and the in-situ oxidation of a primary ore fluid in specific structural settings. Phase separation and wall-rock carbonation are potentially the most common mechanisms of ore-fluid oxidation and gold precipitation. The influence of multiple gold-depositional mechanisms increases the potential for significant ore-fluid oxidation, and more importantly, provides an effective means of increasing gold endowment. This explains the occurrence of negative δ34S values in ore-related pyrites in some world-class orogenic gold deposits. Sulfur isotopic compositions alone cannot uniquely define potential gold endowment. However, in combination with structural, hydrothermal alteration and fluid inclusion studies that also seek to identify multiple ore-forming processes, they can be a useful indicator. The structural setting of a deposit is also a potentially important factor controlling ore-fluid oxidation and the distribution of δ34S values in ore-related pyrites. At Victory-Defiance, the occurrence of negative δ34S(py) values in gently-dipping dilational structures, compared to more positive δ34S(py) values in steeply-dipping compressional structures, is potentially associated with different gold-depositional mechanisms that developed as a result of fluid-pressure fluctuations during different stages of the fault-valve cycle. During the pre-failure stage, when fluids are discharging from faults, fluid-rock interaction is the dominant gold-depositional mechanism. Phase separation and back-mixing of modified ore-fluid components are dominant during and immediately after faulting. Under appropriate conditions, any, or all, of these three mechanisms can oxidize orogenic gold fluids and cause gold deposition. The influence of multiple gold-depositional mechanisms during fault-valve cycles at dilational jogs, where fluid pressure fluctuations are interpreted to be most severe, can potentially explain both the large gold endowment of the giant to world-class Golden Mile, New Celebration and Victory-Defiance deposits along the Boulder-Lefroy Shear Zone, and the presence of gold-related pyrites with negative δ34S values in these deposits. This study highlights the interplay that exists between physical and chemical processes in orogenic gold Mineral Systems, during the transport of ore fluids in pathways from original fluid reservoirs to deposit sites. Potentially, a single and widespread orogenic ore-fluid could become oxidized, and lead to the formation of ore-related sulfides with variable sulfur isotopic compositions, depending on the nature and orientation of major fluid pathways, the nature of wall-rocks through which it circulates, and the precise ore-depositional processes that develop during fault-valve cycles.