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Description
Volcanic eruptions can be serious geologic hazards, and have the potential to effect human life, infrastructure, and climate. Therefore, an understanding of the evolution and conditions of the magmas stored beneath volcanoes prior to their eruption is crucial for the ability to monitor such systems and develop effective hazard mitigation plans. This dissertation combines classic petrologic tools such as mineral chemistry and thermometry with novel techniques such as diffusion chronometry and statistical modeling in order to better understand the processes and timing associated with volcanic eruptions. By examining zoned crystals from the fallout ash of Yellowstone’s most recent supereruption, my work shows that the rejuvenation of magma has the ability to trigger a catastrophic supereruption at Yellowstone caldera in the years (decades at most) prior to eruption. This provides one of the first studies to thoroughly identify a specific eruption trigger of a past eruption using the crystal record. Additionally, through experimental investigation, I created a novel diffusion chronometer with application to determine magmatic timescales in silicic volcanic systems (i.e., rhyolite/dacite). My results show that Mg-in-sanidine diffusion operates simultaneously by both a fast and slow diffusion path suggesting that experimentally-derived diffusion chronometers may be more complex than previously thought. When applying Mg-in-sanidine chronometry to zoned sanidine from the same supereruption at Yellowstone, the timing between rejuvenation and eruption is further resolved to as short as five months, providing a greater understanding of the timing of supereruption triggers. Additionally, I developed a new statistical model to examine the controls on a single volcano’s distribution of eruptions through time, therefore the controls on the timing between successive eruptions, or repose time. When examining six Cascade volcanoes with variable distribution patterns through time, my model shows these distributions are not result of sampling bias, rather may represent geologic processes. There is a robust negative correlation between average repose time and average magma composition (i.e., SiO2), suggesting this may be a controlling factor of long-term repose time at Cascade volcanoes. Together, my work provides a better vision for forecasting models to mitigate potential destruction.
ContributorsShamloo, Hannah (Author) / Till, Christy (Thesis advisor) / Hervig, Richard (Committee member) / Barboni, Melanie (Committee member) / Shock, Everett (Committee member) / Shim, Sang-Heon (Committee member) / Arizona State University (Publisher)
Created2020
Description
Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to petroleum generation and to chemoautotrophic microbial communities. There have been numerous studies on the reactivity of organic compounds in water at elevated temperatures, but these studies rarely explore the consequences of inorganic solutes in hydrothermal fluids. The experiments in this thesis explore new reaction pathways of organic compounds mediated by aqueous and solid phase metals, mainly Earth-abundant copper. These experiments show that copper species have the potential to oxidize benzene and toluene, which are typically viewed as unreactive. These pathways add to the growing list of known organic transformations that are possible in natural hydrothermal systems. In addition to the characterization of reactions in natural systems, there has been recent interest in using hydrothermal conditions to facilitate organic transformations that would be useful in an applied, industrial or synthetic setting. This thesis identifies two sets of conditions that may serve as alternatives to commonplace industrial processes. The first process is the oxidation of benzene with copper to form phenol and chlorobenzene. The second is the copper mediated dehalogenation of aryl halides. Both of these processes apply the concepts of geomimicry by carrying out organic reactions under Earth-like conditions. Only water and copper are needed to implement these processes and there is no need for exotic catalysts or toxic reagents.
ContributorsLoescher, Grant (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2020
Description
Due to analytical limitations, thermodynamic modeling is a lucrative alternative for obtaining metal speciation in chemically complex systems like life. However, such modeling is limited by the lack of equilibrium constant data for metal-complexation reactions, particularly for metal-organic species. These problems were ameliorated estimating these properties from 0-125°C for ~18,000 metal complexes of small molecules, proteins and peptides.
The estimates of metal-ligand equilibrium constants at 25°C and 1 bar were made using multiple linear free energy relationships in accordance with the metal-coordinating properties of ligands such as denticity, identity of electron donor group, inductive effects and steric hindrance. Analogous relationships were made to estimated metal-ligand complexation entropy that facilitated calculation of equilibrium constants up to 125°C using the van’t Hoff equation. These estimates were made for over 250 ligands that include carboxylic acids, phenols, inorganic acids, amino acids, peptides and proteins.
The stability constants mentioned above were used to obtain metal speciation in several microbial growth media including past bioavailability studies and compositions listed on the DSMZ website. Speciation calculations were also carried out for several metals in blood plasma and cerebrospinal fluid that include metals present at over micromolar abundance (sodium, potassium, calcium, magnesium, iron, copper and zinc) and metals of therapeutic or toxic potential (like gallium, rhodium and bismuth). Metal speciation was found to be considerably dependent on pH and chelator concentration that can help in the selection of appropriate ligands for gallium & rhodium based anticancer drugs and zinc-based antidiabetics. It was found that methanobactin can considerably alter copper speciation and is therefore a suitable agent for the treatment of Wilson Disease. Additionally, bismuth neurotoxicity was attributed to the low transferrin concentration in cerebrospinal fluid and the predominance of aqueous bismuth trihydroxide. These results demonstrate that metal speciation calculations using thermodynamic modeling can be extremely useful for understanding metal bioavailability in microbes and human bodily fluids.
The estimates of metal-ligand equilibrium constants at 25°C and 1 bar were made using multiple linear free energy relationships in accordance with the metal-coordinating properties of ligands such as denticity, identity of electron donor group, inductive effects and steric hindrance. Analogous relationships were made to estimated metal-ligand complexation entropy that facilitated calculation of equilibrium constants up to 125°C using the van’t Hoff equation. These estimates were made for over 250 ligands that include carboxylic acids, phenols, inorganic acids, amino acids, peptides and proteins.
The stability constants mentioned above were used to obtain metal speciation in several microbial growth media including past bioavailability studies and compositions listed on the DSMZ website. Speciation calculations were also carried out for several metals in blood plasma and cerebrospinal fluid that include metals present at over micromolar abundance (sodium, potassium, calcium, magnesium, iron, copper and zinc) and metals of therapeutic or toxic potential (like gallium, rhodium and bismuth). Metal speciation was found to be considerably dependent on pH and chelator concentration that can help in the selection of appropriate ligands for gallium & rhodium based anticancer drugs and zinc-based antidiabetics. It was found that methanobactin can considerably alter copper speciation and is therefore a suitable agent for the treatment of Wilson Disease. Additionally, bismuth neurotoxicity was attributed to the low transferrin concentration in cerebrospinal fluid and the predominance of aqueous bismuth trihydroxide. These results demonstrate that metal speciation calculations using thermodynamic modeling can be extremely useful for understanding metal bioavailability in microbes and human bodily fluids.
ContributorsPrasad, Apar (Author) / Shock, Everett (Thesis advisor) / Trovitch, Ryan (Committee member) / Redding, Kevin (Committee member) / Arizona State University (Publisher)
Created2019
Description
Sulfur oxidation is a process that is seen a wide variety of places. One particular place is Yellowstone national park where an abundance of hot springs are present. These acidic and hot places are prime locations for sulfur oxidation to occur. At a very basic level this is thought of as Sulfur, oxygen, and water forming sulfate and hydrogen. Many other reactions occur when an organism performs these processes, and many enzymes are used for this. This paper aimed to create, balance, and analyze the reactions involved in the paper Sulfur Oxidation in the Acidophilic Autotrophic Acidithiobacillus spp. (Wang et al., 2019) Once these reactions were balanced thermodynamic properties were found to evaluate the Gibbs Free Energy of these reactions. This allowed for a unique energy-based view of how this web of reactions relate to each other.
ContributorsMolina, Johnathan (Author) / Shock, Everett (Thesis director) / Weeks, Katelyn (Committee member) / Barrett, The Honors College (Contributor) / School of Molecular Sciences (Contributor)
Created2021-12
Description
Evaluations of chemical energy supplies for redox reactions used by chemotrophs in water-rock hosted ecosystems are often done separately from evaluations of chemotroph diversity. However, given that energy is a fundamental and unifying parameter for life, much can be gained by evaluating chemical energy as an ecological parameter of water-rock hosted ecosystems. Therefore, I developed an approach that combines evaluation of chemical energy supplies with 16S and 18S rRNA gene amplicon sequencing. I used this approach to assess drivers of microbial distribution, diversity and activity in serpentinized fluids of the Samail Ophiolite of Oman and in hot springs in Yellowstone National Park.
Through the application of the approach, microbiological interactions in serpentinized fluids were found to be more complex than anticipated. Serpentinized fluids are hyperalkaline and pH is often considered the driving parameter of microbial diversity, however hydrogenotrophic community composition varies in hyperalkaline fluids with similar pH. The composition of hydrogenotrophic communities in serpentinized fluids were found to correspond to the availability of the electron acceptor for hydrogenotrophic redox reactions. Specifically, hydrogenotrophic community composition transitions from being dominated by the hydrogenotrophic methanogen genus, Methanobacterium, when the concentration of sulfate is less than ~10 μm. Above ~10 μm, sulfate reducers are most abundant. Additionally, Methanobacterium was found to co-occur with the protist genus, Cyclidium, in serpentinized fluids. Species of Cyclidium are anaerobic and known to have methanogen endosymbionts. Therefore, Cyclidium may supply inorganic carbon evolved from fermentation to Methanobacterium, thereby mitigating pH dependent inorganic carbon limitation.
This approach also revealed possible biological mechanisms for methane oxidation in Yellowstone hot springs. Measurable rates of biological methane oxidation in hot spring sediments are likely associated with methanotrophs of the phylum, Verrucomicrobia, and the class, Alphaproteobacteria. Additionally, rates were measurable where known methanotrophs were not detected. At some of these sites, archaeal ammonia oxidizer taxa were detected. Ammonia oxidizers have been shown to be capable of methane oxidation in other systems and may be an alternative mechanism for methanotrophy in Yellowstone hot springs. At the remaining sites, uncharacterized microbial lineages may be capable of carrying out methane oxidation in Yellowstone hot springs.
Through the application of the approach, microbiological interactions in serpentinized fluids were found to be more complex than anticipated. Serpentinized fluids are hyperalkaline and pH is often considered the driving parameter of microbial diversity, however hydrogenotrophic community composition varies in hyperalkaline fluids with similar pH. The composition of hydrogenotrophic communities in serpentinized fluids were found to correspond to the availability of the electron acceptor for hydrogenotrophic redox reactions. Specifically, hydrogenotrophic community composition transitions from being dominated by the hydrogenotrophic methanogen genus, Methanobacterium, when the concentration of sulfate is less than ~10 μm. Above ~10 μm, sulfate reducers are most abundant. Additionally, Methanobacterium was found to co-occur with the protist genus, Cyclidium, in serpentinized fluids. Species of Cyclidium are anaerobic and known to have methanogen endosymbionts. Therefore, Cyclidium may supply inorganic carbon evolved from fermentation to Methanobacterium, thereby mitigating pH dependent inorganic carbon limitation.
This approach also revealed possible biological mechanisms for methane oxidation in Yellowstone hot springs. Measurable rates of biological methane oxidation in hot spring sediments are likely associated with methanotrophs of the phylum, Verrucomicrobia, and the class, Alphaproteobacteria. Additionally, rates were measurable where known methanotrophs were not detected. At some of these sites, archaeal ammonia oxidizer taxa were detected. Ammonia oxidizers have been shown to be capable of methane oxidation in other systems and may be an alternative mechanism for methanotrophy in Yellowstone hot springs. At the remaining sites, uncharacterized microbial lineages may be capable of carrying out methane oxidation in Yellowstone hot springs.
ContributorsHowells, Alta Emily Gessner (Author) / Shock, Everett (Thesis advisor) / Collins, James (Committee member) / Anbar, Ariel (Committee member) / Cadillo-Quiroz, Hinsby (Committee member) / Arizona State University (Publisher)
Created2020
Description
Despite his critical role in the development of American Surrealism, Abstract Expressionism, and Postwar Assemblage, gay Filipino-American artist Alfonso Ossorio remains at the margins of the historiography of these movements. Born in Manila, Philippines, the artist immigrated to the United States in 1930 where he lived and worked until his death in 1990 at his home city of East Hampton, New York. He is among the few Philippine-descended artists living in 20th-century America producing museum-collected works. Since America’s colonial occupation of the Philippines in the 19th-century, immigration has been increasing as a result of migrant labor, military recruitment, and economic exchange. However, the Philippine diaspora’s artistic contributions and visual identity before 1980 are largely under-researched in the United States. Queer artists of color, especially Filipinx-Americans, rarely feature in the dominant narratives of American modernity. Ossorio deeply inflected the trajectory of the American avant-garde yet his marginal place in the history demonstrates how art communities excluded queer and Philippine-American identities in the 20th-century during the development of two major American modernist movements. The scholarship has increased since Ossorio’s death in 1990 as a result of museum and gallery exhibitions. Previous writers focus on biographical description or contextualize Ossorio’s work within a broad movement category without considering Ossorio’s Filipino-American and gay identities in advanced detail from queer and critical race frameworks. These studies lack specific theoretical analysis around race, sexuality, and colonialism on Ossorio’s identity and his artistic communities. Through the analysis of his paintings and archival documents, this thesis argues that Ossorio’s negotiation of these intersecting minority categories is central to understanding his artistic production and his relationship to the American avant-garde. This research applies the current literature on queer theory, critical race theory, and postcolonial theory on Filipinx-American identity to Ossorio’s life and artwork. I center the work of Philippine psychologist Virgilio G. Enriquez with additions from Filipinx-American scholars Martin F. Manalansan IV, Vicente Rafael, Denise Cruz and American scholars art historian Richard Meyer and queer theorist Judith Butler when examining the artworks Untitled 1944 (1944) and Astonished Mother (1950) in the context of Surrealism and Abstract Expressionism respectively.
ContributorsMiranda, Matthew Villar (Author) / Afanador-Pujol, Angélica J. (Thesis advisor) / Mesch, Claudia (Committee member) / Bailey, Marlon M. (Committee member) / Guevarra Jr., Rudy P. (Committee member) / Arizona State University (Publisher)
Created2021
Description
Shirin Neshat is recognized as the most prominent artist of the Iranian diaspora. Her two photographic series, Women of Allah (1993-97) and The Book of Kings (2012), are both reactions to the socio-political events and the change of female identity in Iran. The search for Iranian identity has a long tradition in Iranian photography. Neshat's figures, with their penetrating gazes, heavy draperies, and body postures, make reference to nineteenth-century Qajar photography. Through various cultural elements in her artworks, Neshat critiques oppression in Iranian society. Neshat employs and inscribes Persian poetry to communicate contradiction within Iranian culture.
To read Neshat’s photography, it is crucial to register her use of Persian language and historical poetry. Although the reading and understanding of the Persian texts Neshat inscribes on her photographs plays a fundamental role in the interpretation of her work, Neshat’s artworks are not entirely conceptual. The lack of translation of these included texts in Neshat’s exhibitions indicates a decorative use of Persian calligraphy. The Western eye can aesthetically explore this exotic Eastern decorative calligraphy. The formal qualities of Neshat’s photographs remain, even if the viewer is unable to read or understand the Persian texts.
To read Neshat’s photography, it is crucial to register her use of Persian language and historical poetry. Although the reading and understanding of the Persian texts Neshat inscribes on her photographs plays a fundamental role in the interpretation of her work, Neshat’s artworks are not entirely conceptual. The lack of translation of these included texts in Neshat’s exhibitions indicates a decorative use of Persian calligraphy. The Western eye can aesthetically explore this exotic Eastern decorative calligraphy. The formal qualities of Neshat’s photographs remain, even if the viewer is unable to read or understand the Persian texts.
ContributorsBokharachi, Elnaz (Author) / Mesch, Claudia (Thesis advisor) / Hoy, Meredith (Committee member) / Anand, Julie (Committee member) / Ghanem, Carla (Committee member) / Arizona State University (Publisher)
Created2015
Description
Ethnogeology is the scientific study of human relationships with the Earth as a system, typically conducted within the context of a specific culture. Indigenous or historically resident people may perceive local places differently from outside observers trained in the Western tradition. Ethnogeologic knowledge includes traditional indigenous knowledge (alternatively referred to as traditional ecological knowledge or TEK), which exceeds the boundaries of non-Indigenous ideas of physical characteristics of the world, tends to be more holistic, and is culturally framed. In this ethnogeological study, I have implemented several methods of participatory rapid assessment (PRA) from the discipline of field ethnography to collect culturally framed geological knowledge, as well to measure the authenticity of the knowledge collected. I constructed a cultural consensus model (CCM) about karst as a domain of knowledge. The study area is located in the karst physiographic region of the Caribbean countries of the Dominican Republic (DR) and Puerto Rico (PR). Ethnogeological data collected and analyzed using CCM satisfied the requirements of a model where I have found statistically significance among participant’s agreement and competence values. Analysis of the competence means in the population of DR and PR results in p < 0.05 validating the methods adapted for this study. I discuss the CCM for the domain of karst (in its majority) that is shared among consultants in the countries of PR and the DR that is in the form of metaphors and other forms of culturally framed descriptions. This work continuing insufficient representation of minority groups such as Indigenous people, Native Americans, Alaska Natives, and Hispanic/Latinxs in the Earth Sciences.
ContributorsGarcia, Angel Antonio (Author) / Semken, Steven (Thesis advisor) / Brandt, Elizabeth, (Committee member) / Shock, Everett (Committee member) / Bowman, Catherine (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2018
Description
Urbanization and woody plant encroachment, with subsequent brush management, are two significant land cover changes that are represented in the southwestern United States. Urban areas continue to grow, and rangelands are undergoing vegetation conversions, either purposely through various rangeland management techniques, or by accident, through inadvertent effects of climate and management. This thesis investigates how areas undergoing land cover conversions in a semiarid region, through urbanization or rangeland management, influences energy, water and carbon fluxes. Specifically, the following scientific questions are addressed: (1) what is the impact of different urban land cover types in Phoenix, AZ on energy and water fluxes?, (2) how does the land cover heterogeneity influence energy, water, and carbon fluxes in a semiarid rangeland undergoing woody plant encroachment?, and (3) what is the impact of brush management on energy, water, and carbon fluxes?
The eddy covariance technique is well established to measure energy, water, and carbon fluxes and is used to quantify and compare flux measurements over different land surfaces. Results reveal that in an urban setting, paved surfaces exhibit the largest sensible and lowest latent heat fluxes in an urban environment, while a mesic landscape exhibits the largest latent heat fluxes, due to heavy irrigation. Irrigation impacts flux sensitivity to precipitation input, where latent heat fluxes increase with precipitation in xeric and parking lot landscapes, but do not impact the mesic system. In a semiarid managed rangeland, past management strategies and disturbance histories impact vegetation distribution, particularly the distribution of mesquite trees. At the site with less mesquite coverage, evapotranspiration (ET) is greater, due to greater grass cover. Both sites are generally net sinks of CO2, which is largely dependent on moisture availability, while the site with greater mesquite coverage has more respiration and generally greater gross ecosystem production (GEP). Initial impacts of brush management reveal ET and GEP decrease, due to the absence of mesquite trees. However the impact appears to be minimal by the end of the productive season. Overall, this dissertation advances the understanding of land cover change impacts on surface energy, water, and carbon fluxes in semiarid ecosystems.
The eddy covariance technique is well established to measure energy, water, and carbon fluxes and is used to quantify and compare flux measurements over different land surfaces. Results reveal that in an urban setting, paved surfaces exhibit the largest sensible and lowest latent heat fluxes in an urban environment, while a mesic landscape exhibits the largest latent heat fluxes, due to heavy irrigation. Irrigation impacts flux sensitivity to precipitation input, where latent heat fluxes increase with precipitation in xeric and parking lot landscapes, but do not impact the mesic system. In a semiarid managed rangeland, past management strategies and disturbance histories impact vegetation distribution, particularly the distribution of mesquite trees. At the site with less mesquite coverage, evapotranspiration (ET) is greater, due to greater grass cover. Both sites are generally net sinks of CO2, which is largely dependent on moisture availability, while the site with greater mesquite coverage has more respiration and generally greater gross ecosystem production (GEP). Initial impacts of brush management reveal ET and GEP decrease, due to the absence of mesquite trees. However the impact appears to be minimal by the end of the productive season. Overall, this dissertation advances the understanding of land cover change impacts on surface energy, water, and carbon fluxes in semiarid ecosystems.
ContributorsTempleton, Nicole Pierini (Author) / Vivoni, Enrique R (Thesis advisor) / Archer, Steven R (Committee member) / Mascaro, Giuseppe (Committee member) / Scott, Russell L. (Committee member) / Wang, Zhi-Hua (Committee member) / Arizona State University (Publisher)
Created2017