Matching Items (3)
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- All Subjects: Carbon Sequestration
- All Subjects: Bipyridine
- All Subjects: Geographic information systems
- Creators: Dorn, Ronald
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
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
Description
This work investigates the effects of non-random sampling on our understanding of species distributions and their niches. In its most general form, bias is systematic error that can obscure interpretation of analytical results by skewing samples away from the average condition of the system they represent. Here I use species distribution modelling (SDM), virtual species, and multiscale geographically weighted regression (MGWR) to explore how sampling bias can alter our perception of broad patterns of biodiversity by distorting spatial predictions of habitat, a key characteristic in biogeographic studies. I use three separate case studies to explore: 1) How methods to account for sampling bias in species distribution modeling may alter estimates of species distributions and species-environment relationships, 2) How accounting for sampling bias in fossil data may change our understanding of paleo-distributions and interpretation of niche stability through time (i.e. niche conservation), and 3) How a novel use of MGWR can account for environmental sampling bias to reveal landscape patterns of local niche differences among proximal, but non-overlapping sister taxa. Broadly, my work shows that sampling bias present in commonly used federated global biodiversity observations is more than enough to degrade model performance of spatial predictions and niche characteristics. Measures commonly used to account for this bias can negate much loss, but only in certain conditions, and did not improve the ability to correctly identify explanatory variables or recreate species-environment relationships. Paleo-distributions calibrated on biased fossil records were improved with the use of a novel method to directly estimate the biased sampling distribution, which can be generalized to finer time slices for further paleontological studies. Finally, I show how a novel coupling of SDM and MGWR can illuminate local differences in niche separation that more closely match landscape genotypic variability in the two North American desert tortoise species than does their current taxonomic delineation.
ContributorsInman, Richard (Author) / Franklin, Janet (Thesis advisor) / Fotheringham, A. Stewart (Committee member) / Dorn, Ronald (Committee member) / Arizona State University (Publisher)
Created2018