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Description
Growth of the Phoenix metropolitan area led to exposures of the internal bedrock structure of surrounding semi-arid mountain ranges as housing platforms or road cuts. Such exposures in the Sonoran and Mojave deserts reveal the presence of sedimentary calcium carbonate infilling the pre-existing fracture matrix of the bedrock. Field surveys

Growth of the Phoenix metropolitan area led to exposures of the internal bedrock structure of surrounding semi-arid mountain ranges as housing platforms or road cuts. Such exposures in the Sonoran and Mojave deserts reveal the presence of sedimentary calcium carbonate infilling the pre-existing fracture matrix of the bedrock. Field surveys of bedrock fractures filled with carbonate (BFFC) reveal an average of 0.079 +/- 0.024 mT C/m2 stored in the upper 2 m of analyzed bedrock exposures. Back-scattered electron microscopy images indicate the presence of carbonate at the micron scale, not included in this estimation. Analysis of the spatial extent of bedrock landforms in arid and semi-arid regions worldwide suggests that ~1485 GtC could potentially be stored in the upper 2 m horizon of BFFCs. Radiocarbon dating obtained at one of the sites indicates it is likely that some of the carbonate was flushed into the bedrock system during glacial wet pulses, and is stored on Pleistocene timescales or longer. Strontium isotope analysis at the same site suggest the potential for a substantial cation contribution from weathering of the local bedrock, indicating the potential exists for sequestration of atmospheric carbon in BFFCs. Rates of carbon release from BFFCs are tied to rates of erosion of bedrock ranges in desert climates.
ContributorsHarrison, Emma (Author) / Dorn, Ronald (Thesis advisor) / Reynolds, Stephen (Committee member) / Schmeeckle, Mark (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based

Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Carbon Capture and Storage (CCS) is a climate stabilization strategy that prevents CO2 emissions from entering the atmosphere. Despite its benefits, impactful CCS projects require large investments in infrastructure, which could deter governments from implementing this strategy. In this sense, the development of innovative tools to support large-scale cost-efficient CCS

Carbon Capture and Storage (CCS) is a climate stabilization strategy that prevents CO2 emissions from entering the atmosphere. Despite its benefits, impactful CCS projects require large investments in infrastructure, which could deter governments from implementing this strategy. In this sense, the development of innovative tools to support large-scale cost-efficient CCS deployment decisions is critical for climate change mitigation. This thesis proposes an improved mathematical formulation for the scalable infrastructure model for CCS (SimCCS), whose main objective is to design a minimum-cost pipe network to capture, transport, and store a target amount of CO2. Model decisions include source, reservoir, and pipe selection, as well as CO2 amounts to capture, store, and transport. By studying the SimCCS optimal solution and the subjacent network topology, new valid inequalities (VI) are proposed to strengthen the existing mathematical formulation. These constraints seek to improve the quality of the linear relaxation solutions in the branch and bound algorithm used to solve SimCCS. Each VI is explained with its intuitive description, mathematical structure and examples of resulting improvements. Further, all VIs are validated by assessing the impact of their elimination from the new formulation. The validated new formulation solves the 72-nodes Alberta problem up to 7 times faster than the original model. The upgraded model reduces the computation time required to solve SimCCS in 72% of randomly generated test instances, solving SimCCS up to 200 times faster. These formulations can be tested and then applied to enhance variants of the SimCCS and general fixed-charge network flow problems. Finally, an experience from testing a Benders decomposition approach for SimCCS is discussed and future scope of probable efficient solution-methods is outlined.
ContributorsLobo, Loy Joseph (Author) / Sefair, Jorge A (Thesis advisor) / Escobedo, Adolfo (Committee member) / Kuby, Michael (Committee member) / Middleton, Richard (Committee member) / Arizona State University (Publisher)
Created2017