Matching Items (3)
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- All Subjects: Carbon Sequestration
- All Subjects: Bipyridine
- All Subjects: Riparian ecology
- Genre: Academic theses
- Creators: Dorn, Ronald
- Status: Published
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 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
Description
Ephemeral streams in Arizona that are perpendicularly intersected by the Central Arizona Project (CAP) canal have been altered due to partial or complete damming of the stream channel. The dammed upstream channels have experienced decades long cycles of sediment deposition and waterlogging during storm events causing the development of "green-up" zones. This dissertation examines the biogeomorphological effects of damming ephemeral streams caused by the CAP canal by investigating: (1) changes in the preexisting spatial cover of riparian vegetation and how these changes are affected by stream geometry; (2) green-up initiation and evolution; and (3) changes in plant species and community level changes. To the author's knowledge, this is the only study that undertakes an interdisciplinary approach to understanding the environmental responses to anthropogenically-altered ephemeral stream channels. The results presented herein show that vegetation along the upstream section increased by an average of 200,872 m2 per kilometer of the CAP canal over a 28 year period. Vegetation growth was compared to channel widths which share a quasi-linear relationship. Remote sensing analysis of Landsat TM images using an object-oriented approach shows that riparian vegetation cover gradually increased over 28 years. Field studies reveal that the increases in vegetation are attributed to the artificial rise in local base-level upstream created by the canal, which causes water to spill laterally onto the desert floor. Vegetation within the green-up zone varies considerably in comparison to pre-canal construction. Changes are most notable in vegetation community shifts and abundance. The wettest section of the green-up zone contains the greatest density of woody plant stems, the greatest vegetation volume, and a high percentage of herbaceous cover. Vegetation within wetter zones changed from a tree-shrub to a predominantly tree-herb assemblage, whereas desert shrubs located in zones with intermediate moisture have developed larger stems. Results from this study lend valuable insight to green-up processes associated with damming ephemeral streams, which can be applied to planning future canal or dam projects in drylands. Also, understanding the development of the green-up zones provide awareness to potentially avoiding flood damage to infrastructure that may be unknowingly constructed within the slow-growing green-up zone.
ContributorsHamdan, Abeer (Author) / Schmeeckle, Mark (Thesis advisor) / Myint, Soe (Thesis advisor) / Dorn, Ronald (Committee member) / Stromberg, Juliet (Committee member) / Arizona State University (Publisher)
Created2014
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 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