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This dissertation examines two topics of emerging interest in the field of organic geochemistry. The topic of the first portion of the dissertation is cold organic geochemistry on Saturn's moon Titan. Titan has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most

This dissertation examines two topics of emerging interest in the field of organic geochemistry. The topic of the first portion of the dissertation is cold organic geochemistry on Saturn's moon Titan. Titan has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most famously as lakes. Photochemical reactions produce solid organics in Titan's atmosphere, and these materials settle onto the surface. At the surface, liquids can interact with solids, and geochemical processes can occur. To better understand these processes, I developed a thermodynamic model that can be used to calculate the solubilities of gases and solids in liquid hydrocarbons at cryogenic temperatures. The model was parameterized using experimental data, and provides a good fit to the data. Application of the model to Titan reveals that the equilibrium composition of surface liquids depends on the abundance of methane in the local atmosphere. The model also indicates that solid acetylene should be quite soluble in surface liquids, which implies that acetylene-rich rocks should be susceptible to chemical erosion, and acetylene evaporites may form on Titan. In the latter half of this dissertation, I focus on hot organic geochemistry below the surface of the Earth. Organic compounds are common in sediments. Burial of sediments leads to changes in physical and chemical conditions, promoting organic reactions. An important organic reaction in subsurface environments is decarboxylation, which generates hydrocarbons and carbon dioxide from simple organic acids. Fundamental knowledge about decarboxylation is required to better understand how the organic and inorganic compositions of sediments evolve in response to changing geochemical conditions. I performed experiments with the model compound phenylacetic acid to obtain information about mechanisms of decarboxylation in hydrothermal fluids. Patterns in rates of decarboxylation of substituted phenylacetic acids point to a mechanism that proceeds through a ring-protonated zwitterion of phenylacetic acid. In contrast, substituted sodium phenylacetates exhibit a different kinetic pattern, one that is consistent with the formation of the benzyl anion as an intermediate. Results from experiments with added hydrochloric acid or sodium hydroxide, and deuterated water agree with these interpretations. Thus, speciation dictates mechanism of decarboxylation.
ContributorsGlein, Christopher R (Author) / Shock, Everett L (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Zolotov, Mikhail Y (Committee member) / Williams, Lynda B (Committee member) / Gould, Ian R (Committee member) / Arizona State University (Publisher)
Created2012
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The discovery and development of novel antibacterial agents is essential to address the rising health concern over antibiotic resistant bacteria. This research investigated the antibacterial activity of a natural clay deposit near Crater Lake, Oregon, that is effective at killing antibiotic resistant human pathogens. The primary rock types in the

The discovery and development of novel antibacterial agents is essential to address the rising health concern over antibiotic resistant bacteria. This research investigated the antibacterial activity of a natural clay deposit near Crater Lake, Oregon, that is effective at killing antibiotic resistant human pathogens. The primary rock types in the deposit are andesitic pyroclastic materials, which have been hydrothermally altered into argillic clay zones. High-sulfidation (acidic) alteration produced clay zones with elevated pyrite (18%), illite-smectite (I-S) (70% illite), elemental sulfur, kaolinite and carbonates. Low-sulfidation alteration at neutral pH generated clay zones with lower pyrite concentrations pyrite (4-6%), the mixed-layered I-S clay rectorite (R1, I-S) and quartz.

Antibacterial susceptibility testing reveals that hydrated clays containing pyrite and I-S are effective at killing (100%) of the model pathogens tested (E. coli and S. epidermidis) when pH (< 4.2) and Eh (> 450 mV) promote pyrite oxidation and mineral dissolution, releasing > 1 mM concentrations of Fe2+, Fe3+ and Al3+. However, certain oxidized clay zones containing no pyrite still inhibited bacterial growth. These clays buffered solutions to low pH (< 4.7) and oxidizing Eh (> 400 mV) conditions, releasing lower amounts (< 1 mM) of Fe and Al. The presence of carbonate in the clays eliminated antibacterial activity due to increases in pH, which lower pyrite oxidation and mineral dissolution rates.

The antibacterial mechanism of these natural clays was explored using metal toxicity and genetic assays, along with advanced bioimaging techniques. Antibacterial clays provide a continuous reservoir of Fe2+, Fe3+ and Al3+ that synergistically attack pathogens while generating hydrogen peroxide (H2O¬2). Results show that dissolved Fe2+ and Al3+ are adsorbed to bacterial envelopes, causing protein misfolding and oxidation in the outer membrane. Only Fe2+ is taken up by the cells, generating oxidative stress that damages DNA and proteins. Excess Fe2+ oxidizes inside the cell and precipitates Fe3+-oxides, marking the sites of hydroxyl radical (•OH) generation. Recognition of this novel geochemical antibacterial process should inform designs of new mineral based antibacterial agents and could provide a new economic industry for such clays.
ContributorsMorrison, Keith D (Author) / Williams, Lynda B (Thesis advisor) / Williams, Stanley N (Thesis advisor) / Misra, Rajeev (Committee member) / Shock, Everett (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2015
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Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines

Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines the fidelity of 238U/235U in sedimentary carbonate rocks as a paleoredox proxy focusing on the following issues: (1) U isotope fractionation during U incorporation into primary abiotic and biogenic calcium carbonates; (2) diagenetic effects on U isotope fractionation in modern shallow-water carbonate sediments; (3) the effects of anoxic depositional environments on 238U/235U in carbonate sediments.

Variable and positive shifts of 238U/235U were observed during U uptake by primary abiotic and biotic calcium carbonates, carbonate diagenesis, and anoxic deposition of carbonates. Previous CaCO3 coprecipitation experiments demonstrated a small but measurable U isotope fractionation of ~0.10 ‰ during U(VI) incorporation into abiotic calcium carbonates, with 238U preferentially incorporated into the precipitates (Chen et al., 2016). The magnitude of U isotope fractionation depended on aqueous U speciation, which is controlled by water chemistry, including pH, ionic strength, carbonate, and Ca2+ and Mg2+ concentrations. Based on this speciation-dependent isotope fractionation model, the estimated U isotope fractionation in abiotic calcium carbonates induced by secular changes in seawater chemistry through the Phanerozoic was predicted to be 0.11–0.23 ‰. A smaller and variable U isotope fractionation (0–0.09 ‰) was observed in primary biogenic calcium carbonates, which fractionated U isotopes in the same direction as abiotic calcium carbonates. Early diagenesis of modern shallow-water carbonate sediments from the Bahamas shifted δ238U values to be 0.270.14 ‰ (1 SD) higher than contemporaneous seawater. Also, carbonate sediments deposited under anoxic conditions in a redox-stratified lake—Fayetteville Green Lake, New York, USA— exhibited elevated δ238U values by 0.160.12 ‰ (1 SD) relative to surface water carbonates with significant enrichments in U.

The significant U isotope fractionation observed in these studies suggests the need to correct for the U isotopic offset between carbonate sediments and coeval seawater when using δ238U variations in ancient carbonate rocks to reconstruct changes in ocean anoxia. The U isotope fractionation in abiotic and biogenic primary carbonate precipitates, during carbonate diagenesis, and under anoxic depositional environments provide a preliminary guideline to calibrate 238U/235U in sedimentary carbonate rocks as a paleoredox proxy.
ContributorsChen, Xinming (Author) / Anbar, Ariel D (Thesis advisor) / Williams, Lynda B (Committee member) / Sharp, Thomas (Committee member) / Hervig, Richard (Committee member) / Romaniello, Stephen (Committee member) / Arizona State University (Publisher)
Created2018
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Many factors are at play within the genome of an organism, contributing to much of the diversity and variation across the tree of life. While the genome is generally encoded by four nucleotides, A, C, T, and G, this code can be expanded. One particular mechanism that we examine in

Many factors are at play within the genome of an organism, contributing to much of the diversity and variation across the tree of life. While the genome is generally encoded by four nucleotides, A, C, T, and G, this code can be expanded. One particular mechanism that we examine in this thesis is modification of bases—more specifically, methylation of Adenine (m6A) within the GATC motif of Escherichia coli. These methylated adenines are especially important in a process called methyl-directed mismatch repair (MMR), a pathway responsible for repairing errors in the DNA sequence produced by replication. In this pathway, methylated adenines identify the parent strand and direct the repair proteins to correct the erroneous base in the daughter strand. While the primary role of methylated adenines at GATC sites is to direct the MMR pathway, this methylation has also been found to affect other processes, such as gene expression, the activity of transposable elements, and the timing of DNA replication. However, in the absence of MMR, the ability of these other processes to maintain adenine methylation and its targets is unknown.
To determine if the disruption of the MMR pathway results in the reduced conservation of methylated adenines as well as an increased tolerance for mutations that result in the loss or gain of new GATC sites, we surveyed individual clones isolated from experimentally evolving wild-type and MMR-deficient (mutL- ;conferring an 150x increase in mutation rate) populations of E. coli with whole-genome sequencing. Initial analysis revealed a lack of mutations affecting methylation sites (GATC tetranucleotides) in wild-type clones. However, the inherent low mutation rates conferred by the wild-type background render this result inconclusive, due to a lack of statistical power, and reveal a need for a more direct measure of changes in methylation status. Thus as a first step to comparative methylomics, we benchmarked four different methylation-calling pipelines on three biological replicates of the wildtype progenitor strain for our evolved populations.
While it is understood that these methylated sites play a role in the MMR pathway, it is not fully understood the full extent of their effect on the genome. Thus the goal of this thesis was to better understand the forces which maintain the genome, specifically concerning m6A within the GATC motif.
ContributorsBoyer, Gwyneth (Author) / Lynch, Michael (Thesis director) / Behringer, Megan (Committee member) / Geiler-Samerotte, Kerry (Committee member) / School of Life Sciences (Contributor) / Department of Psychology (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
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This paper emphasizes how vital prosthetic devices are as tools for both congenital and acquired amputees in order to maximize this population's level of societal productivity, but several issues exist with the current technological focus of development by the prosthetic industry that creates unnecessary hurdles that amputees must surpass in

This paper emphasizes how vital prosthetic devices are as tools for both congenital and acquired amputees in order to maximize this population's level of societal productivity, but several issues exist with the current technological focus of development by the prosthetic industry that creates unnecessary hurdles that amputees must surpass in order to truly benefit from these tools. The first major issue is that these devices are not readily available to all amputees. The astronomical cost of most prosthetic devices is a variable that restricts low income amputee populations from obtaining these vital tools regardless of their level of need, thus highlighting the fact that amputees who are not financially stable are not supported in a fashion that is conducive to their success. Also, cost greatly affects children who suffer from a missing appendage due to the fact that they are in constant need of prosthetic replacement because of physical growth and development. Another issue with the current focus of the prosthetic industry is that it focuses on acquired amputees because this population is much larger in comparison to congenital amputees and thus more lucrative. Congenital amputees' particular needs are often entirely ignored in terms of prosthetic innovation. Finally, low daily utilization is a major issue amongst the amputee population. Several variables exist with the use of prosthetic devices that cause many amputees to decide against the utilization of these tools, like difficulty of use and lack of comfort. This paper will provide solutions to cost, discrimination, issues in development, and daily utilization by emphasizing on how lowering the cost through alternative designs and materials, transitioning the focus of technological development onto the entire amputee population rather than targeting the most lucrative group, and advancing the design in a fashion to which promotes daily utilization will provide the largest level of societal support, so that the amputee population as a whole can maximize their level of productivity in a manner that will allow this group to conquer the hardships that are introduced into their lives due to a missing appendage.
ContributorsO'Connor, Casey Charles (Author) / Popova, Laura (Thesis director) / Graff, Sarah (Committee member) / Department of Psychology (Contributor) / School of Social Work (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
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This study examines Glamour magazine to determine the messages the publication sends to its readers and to evaluate if such messages align with modern feminist goals. The articles of Glamour's 12 issues from the year of 2016 are analyzed using a framework adapted from previous research on women's magazines. Articles

This study examines Glamour magazine to determine the messages the publication sends to its readers and to evaluate if such messages align with modern feminist goals. The articles of Glamour's 12 issues from the year of 2016 are analyzed using a framework adapted from previous research on women's magazines. Articles are coded as either positive (feminist, anti-traditional, promotes equality) or negative (anti-feminist, traditional, promotes inequality). Distinct content themes (appearance, dating, home, self-development, career development, politics/world issues, and entertainment) are also examined individually. After the presentation of data, I examine my findings through a feminist lens to determine the nature of the messages being sent to women through the magazine's editorial content, followed by an assessment of the value of women's magazines and how they could potentially shape the beliefs and roles of a 2017 woman. It is found that about half of the articles in Glamour could be considered as having feminist messages, with strong themes of personal choice, individual empowerment, and political involvement or activism in these articles and throughout the magazine. The content also has many blatantly feminist messages, including consistent use of the word itself. Another 40% of the articles are found to be neutral (no clear message to reader), and the remaining are negative. The sexism inherent in these negative articles is critically examined. Finally, the main takeaways of the findings and their ramifications are discussed from both a media consumer and a media producer perspective, with arguments for why it is important to be critical of a magazine's editorial content.
ContributorsAllnatt, Libby Paige (Author) / Pucci, Jessica (Thesis director) / Dove-Viebahn, Aviva (Committee member) / School of Social Transformation (Contributor) / Department of Psychology (Contributor) / Walter Cronkite School of Journalism and Mass Communication (Contributor) / Barrett, The Honors College (Contributor)
Created2017-12
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Spousal loss is a common, significant life event that can negatively affect multiple facets of individual health and psychological adjustment. Social support is one factor that is shown to improve adjustment following spousal loss, but much less is known regarding which facet of social support is most predictive of positive

Spousal loss is a common, significant life event that can negatively affect multiple facets of individual health and psychological adjustment. Social support is one factor that is shown to improve adjustment following spousal loss, but much less is known regarding which facet of social support is most predictive of positive adjustment outcomes following spousal loss. This study examined the course of changes in mental health and well-being following spousal loss and which facets of social support are associated with better outcomes following spousal loss. Latent growth curve modeling was applied to data from 265 widowed individuals, ages 65 and older, across four assessments (baseline, and 6-, 18-, and 48- months following spousal loss). I examined the following research questions: (1) adjustment following spousal loss will follow a trajectory of an increase in depressive symptoms and anxiety and decrease in well-being with a leveling-off over time, with between-person differences, and (2) emotional support and instrumental support given will lead to more positive adjustment outcomes over time. Depressive symptoms followed the hypothesized trajectory but anxiety and well-being showed relative stability before and after spousal loss. Instrumental support was the most beneficial facet of social support, such that receiving more instrumental support was associated with lower levels of depressive symptoms and anxiety 6-months following spousal loss. Giving more instrumental support led to an increase in well-being following spousal loss. Instrumental support given and received led to increases in well-being as a function of spousal loss. The discussion focuses on whether and how these findings can help to identify ways through which support and help can be given to individuals to improve adjustment to spousal loss and fully recover.
ContributorsSullivan, Colleen Elizabeth (Author) / Infurna, Frank (Thesis director) / Luthar, Suniya (Committee member) / Davis, Mary (Committee member) / Department of Psychology (Contributor) / School of International Letters and Cultures (Contributor) / Barrett, The Honors College (Contributor)
Created2017-12
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Effortful Control (EC) is a person's ability to self-regulate when presented with an environmental stimulus (Rothbart, et al., 2003). It has been well-established that high levels of EC are associated with multiple positive social and academic outcomes in adolescence (Spinrad et al., 2009). Research suggests that parents have a strong

Effortful Control (EC) is a person's ability to self-regulate when presented with an environmental stimulus (Rothbart, et al., 2003). It has been well-established that high levels of EC are associated with multiple positive social and academic outcomes in adolescence (Spinrad et al., 2009). Research suggests that parents have a strong impact on numerous child outcomes, such as EC, through both genetic and environmental pathways. Past research has also examined how parents diagnosed with psychopathology contribute to maladaptive outcomes in their children, including poor regulation, through both genetic and environmental processes (Ellis, et al., 1997). However, less is known about the longitudinal effects of parent dysfunction on the child's environment and regulatory abilities and potential mediators of those effects. The current study tested the hypotheses that parent Alcohol Use Disorder (AUD) would specifically predict early adversity, biological mother conscientiousness, and child EC longitudinally and that early adversity and biological mother conscientiousness would predict child EC. Participants were from a longitudinal study of familial alcoholism (N = 195). Regression analyses indicated that parent AUD was not specifically associated with child EC or with biological mother conscientiousness. However, parent AUD was related to higher levels of early adversity. Additionally, biological mother conscientiousness was associated with higher levels of child EC and early adversity was associated with lower levels of child EC when controlling for earlier EC. Given these findings, future research should test mediation models in which parent AUD predicts child EC indirectly through early adversity.
ContributorsRuof, Ariana Kelsey (Author) / Chassin, Laurie (Thesis director) / Elam, Kit (Committee member) / Davis, Mary (Committee member) / Department of Psychology (Contributor) / Sanford School of Social and Family Dynamics (Contributor) / Barrett, The Honors College (Contributor)
Created2017-12
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Dogs' health and wellbeing is of great importance to their owners. The most common nutritional problem for pet dogs is obesity, with 22-40% of pet dogs being classified as overweight or obese. With many adverse health effects associated with obesity, this is a major concern for owners and veterinarians. The

Dogs' health and wellbeing is of great importance to their owners. The most common nutritional problem for pet dogs is obesity, with 22-40% of pet dogs being classified as overweight or obese. With many adverse health effects associated with obesity, this is a major concern for owners and veterinarians. The degree to which dogs enjoy consuming certain foods can have substantial implications for their body weight, so it is important to understand which aspects of foods make them appealing to dogs. This study aimed to determine whether nutritional aspects of commercial dog foods predict dogs' preferences for those foods. It was found that consumption preference is positively correlated with protein content (p < .001), therefore implying that the protein content of commercial dry dog foods may predict dogs' consumption preferences. Consumption preferences were not predicted by other available measures of food content or caloric value. Dogs' preference for foods high in protein content may be due to the satiating effect of protein. Since foods high in protein both reduce the amount of energy consumed and are found to be palatable to dogs, high-protein dog foods may offer a way for dog food manufacturers, veterinarians, and pet owners to combat obesity in pet dogs.
ContributorsPrevost, Emily Danielle (Author) / Wynne, Clive (Thesis director) / Hall, Nathaniel (Committee member) / School of Life Sciences (Contributor) / Department of Psychology (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
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Musical interpretation is challenging when one's goal is to evoke an emotional response from an audience. In order to develop a well-informed interpretation of Mozart's Fantasia in D minor K. 397, a study was conducted on the historical background of the piece and various performances by well-regarded performers. Fantasias are

Musical interpretation is challenging when one's goal is to evoke an emotional response from an audience. In order to develop a well-informed interpretation of Mozart's Fantasia in D minor K. 397, a study was conducted on the historical background of the piece and various performances by well-regarded performers. Fantasias are written works, but improvisatory by nature. Mozart's fantasias were influenced by C. P. E. Bach's, which included sudden changes in emotion. An Emil Gilels performance provided a classically trained approach, while Mitsuko Uchida's performance provided an emotional approach. Colin Tilney and John Irving performances elucidated the sound of the instruments that Mozart would have been composing with. Altogether, the research culminated in an interpretation of the D minor Fantasia that endeavored to capture the essence of fantasy, improvisation and emotion.
ContributorsMo, Gina Nan (Author) / Emmery, Laura (Thesis director) / Creviston, Hannah (Committee member) / Department of Psychology (Contributor) / School of International Letters and Cultures (Contributor) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05