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This research investigates the biophysical and institutional mechanisms affecting the distribution of metals in the Sonoran Desert of Arizona. To date, a long-term, interdisciplinary perspective on metal pollution in the region has been lacking. To address this gap, I integrated approaches from environmental chemistry, historical geography, and institutional economics to

This research investigates the biophysical and institutional mechanisms affecting the distribution of metals in the Sonoran Desert of Arizona. To date, a long-term, interdisciplinary perspective on metal pollution in the region has been lacking. To address this gap, I integrated approaches from environmental chemistry, historical geography, and institutional economics to study the history of metal pollution in the desert. First, by analyzing the chemistry embodied in the sequentially-grown spines of long-lived cacti, I created a record of metal pollution that details biogeochemical trends in the desert since the 1980s. These data suggest that metal pollution is not simply a legacy of early industrialization. Instead, I found evidence of recent metal pollution in both the heart of the city and a remote, rural location. To understand how changing land uses may have contributed to this, I next explored the historical geography of industrialization in the desert. After identifying cities and mining districts as hot spots for airborne metals, I used a mixture of historical reports, maps, and memoirs to reconstruct the industrial history of these polluted landscapes. In the process, I identified three key transitions in the energy-metal nexus that drove the redistribution of metals from mineral deposits to urban communities. These transitions coincided with the Columbian exchange, the arrival of the railroads, and the economic restructuring that accompanied World War II. Finally, to determine how legal and political forces may be influencing the fate of metals, I studied the evolution of the rights and duties affecting metals in their various forms. This allowed me to track changes in the institutions regulating metals from the mining laws of the 19th century through their treatment as occupational and public health hazards in the 20th century. In the process, I show how Arizona’s environmental and resource institutions were often transformed by extra-territorial concerns. Ultimately, this created an institutional system that compartmentalizes metals and fails to appreciate their capacity to mobilize across legal and biophysical boundaries to accumulate in the environment. Long-term, interdisciplinary perspectives such as this are critical for untangling the complex web of elements and social relations transforming the modern world.
ContributorsHester, Cyrus M (Author) / Larson, Kelli L (Thesis advisor) / Laubichler, Manfred D (Thesis advisor) / MacFadyen, Joshua (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is

Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is the MOF-5 material, specifically its chemical stability in air. The MOF-5 material has a large pore size of 8 Å, and aperture sizes of 15 and 12 Å. The pore size, pore functionality, and physically stable structure makes MOF-5 a desirable material. MOF-5 holds applications in gas/liquid separation, catalysis, and gas storage. The main problem with the MOF-5 material, however, is its instability in atmospheric air. This inherent instability is due to the water in air binding to the zinc-oxide core, effectively changing the material and its structure. Because of this material weakness, the MOF-5 material is difficult to be utilized in industrial applications. Through the research efforts proposed by this study, the stability of the MOF-5 powder and membrane were studied. MOF-5 powder and a MOF-5 membrane were synthesized and characterized using XRD analysis. In an attempt to improve the stability of MOF-5 in air, methyl groups were added to the organic linker in order to hinder the interaction of water with the Zn4O core. This was done by replacing the terepthalic acid organic linker with 2,5-dimethyl terephthalic acid in the powder and membrane synthesis steps. The methyl-modified MOF-5 powder was found to be stable after several days of exposure to air while the MOF-5 powder exhibited significant crystalline change. The methyl-modified membrane was found to be unstable when synthesized using the same procedure as the MOF-5 membrane.
ContributorsAnderson, Anthony David (Author) / Lin, Jerry Y.S. (Thesis director) / Ibrahim, Amr (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
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Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their

Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12