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Phosphorus (P), an essential element for life, is becoming increasingly scarce, and its global management presents a serious challenge. As urban environments dominate the landscape, we need to elucidate how P cycles in urban ecosystems to better understand how cities contribute to — and provide opportunities to solve — problems

Phosphorus (P), an essential element for life, is becoming increasingly scarce, and its global management presents a serious challenge. As urban environments dominate the landscape, we need to elucidate how P cycles in urban ecosystems to better understand how cities contribute to — and provide opportunities to solve — problems of P management. The goal of my research was to increase our understanding of urban P cycling in the context of urban resource management through analysis of existing ecological and socio-economic data supplemented with expert interviews in order to facilitate a transition to sustainable P management. Study objectives were to: I) Quantify and map P stocks and flows in the Phoenix metropolitan area and analyze the drivers of spatial distribution and dynamics of P flows; II) examine changes in P-flow dynamics at the urban agricultural interface (UAI), and the drivers of those changes, between 1978 and 2008; III) compare the UAI's average annual P budget to the global agricultural P budget; and IV) explore opportunities for more sustainable P management in Phoenix. Results showed that Phoenix is a sink for P, and that agriculture played a primary role in the dynamics of P cycling. Internal P dynamics at the UAI shifted over the 30-year study period, with alfalfa replacing cotton as the main locus of agricultural P cycling. Results also suggest that the extent of P recycling in Phoenix is proportionally larger than comparable estimates available at the global scale due to the biophysical characteristics of the region and the proximity of various land uses. Uncertainty remains about the effectiveness of current recycling strategies and about best management strategies for the future because we do not have sufficient data to use as basis for evaluation and decision-making. By working in collaboration with practitioners, researchers can overcome some of these data limitations to develop a deeper understanding of the complexities of P dynamics and the range of options available to sustainably manage P. There is also a need to better connect P management with that of other resources, notably water and other nutrients, in order to sustainably manage cities.
ContributorsMetson, Genevieve (Author) / Childers, Daniel (Thesis advisor) / Aggarwal, Rimjhim (Thesis advisor) / Redman, Charles (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Molybdenum (Mo) is a key trace nutrient for biological assimilation of nitrogen, either as nitrogen gas (N2) or nitrate (NO3-). Although Mo is the most abundant metal in seawater (105 nM), its concentration is low (<5 nM) in most freshwaters today, and it was scarce in the ocean before 600

Molybdenum (Mo) is a key trace nutrient for biological assimilation of nitrogen, either as nitrogen gas (N2) or nitrate (NO3-). Although Mo is the most abundant metal in seawater (105 nM), its concentration is low (<5 nM) in most freshwaters today, and it was scarce in the ocean before 600 million years ago. The use of Mo for nitrogen assimilation can be understood in terms of the changing Mo availability through time; for instance, the higher Mo content of eukaryotic vs. prokaryotic nitrate reductase may have stalled proliferation of eukaryotes in low-Mo Proterozoic oceans. Field and laboratory experiments were performed to study Mo requirements for NO3- assimilation and N2 fixation, respectively. Molybdenum-nitrate addition experiments at Castle Lake, California revealed interannual and depth variability in plankton community response, perhaps resulting from differences in species composition and/or ammonium availability. Furthermore, lake sediments were elevated in Mo compared to soils and bedrock in the watershed. Box modeling suggested that the largest source of Mo to the lake was particulate matter from the watershed. Month-long laboratory experiments with heterocystous cyanobacteria (HC) showed that <1 nM Mo led to low N2 fixation rates, while 10 nM Mo was sufficient for optimal rates. At 1500 nM Mo, freshwater HC hyperaccumulated Mo intercellularly, whereas coastal HC did not. These differences in storage capacity were likely due to the presence in freshwater HC of the small molybdate-binding protein, Mop, and its absence in coastal and marine cyanobacterial species. Expression of the mop gene was regulated by Mo availability in the freshwater HC species Nostoc sp. PCC 7120. Under low Mo (<1 nM) conditions, mop gene expression was up-regulated compared to higher Mo (150 and 3000 nM) treatments, but the subunit composition of the Mop protein changed, suggesting that Mop does not bind Mo in the same manner at <1 nM Mo that it can at higher Mo concentrations. These findings support a role for Mop as a Mo storage protein in HC and suggest that freshwater HC control Mo cellular homeostasis at the post-translational level. Mop's widespread distribution in prokaryotes lends support to the theory that it may be an ancient protein inherited from low-Mo Precambrian oceans.
ContributorsGlass, Jennifer (Author) / Anbar, Ariel D (Thesis advisor) / Shock, Everett L (Committee member) / Jones, Anne K (Committee member) / Hartnett, Hilairy E (Committee member) / Elser, James J (Committee member) / Fromme, Petra (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Black carbon (BC) is the product of incomplete combustion of biomass and fossil fuels. It is found ubiquitously in nature and is relevant to studies in atmospheric science, soil science, oceanography, and anthropology. Black carbon is best described using a combustion continuum that sub-classifies BC into slightly charred biomass, char,

Black carbon (BC) is the product of incomplete combustion of biomass and fossil fuels. It is found ubiquitously in nature and is relevant to studies in atmospheric science, soil science, oceanography, and anthropology. Black carbon is best described using a combustion continuum that sub-classifies BC into slightly charred biomass, char, charcoal and soot. These sub-classifications range in particle size, formation temperature, and relative reactivity. Interest in BC has increased because of its role in the long-term storage of organic matter and the biogeochemistry of urban areas. The global BC budget is unbalanced. Production of BC greatly outweighs decomposition of BC. This suggests that there are unknown or underestimated BC removal processes, and it is likely that some of these processes are occurring in soils. However, little is known about BC reactivity in soil and especially in desert soil. This work focuses on soot BC, which is formed at higher temperatures and has a lower relative reactivity than other forms of BC. Here, I assess the contribution of soot BC to central AZ soils and use the isotopic composition of soot BC to identify sources of soot BC. Soot BC is a significant (31%) fraction of the soil organic matter in central AZ and this work suggests that desert and urban soils may be a storage reservoir for soot BC. I further identify previously unknown removal processes of soot BC found naturally in soil and demonstrate that soil soot BC undergoes abiotic (photo-oxidation) and biotic reactions. Not only is soot BC degraded by these processes, but its chemical composition is altered, suggesting that soot BC contains some chemical moieties that are more reactive than others. Because soot BC demonstrates both refractory and reactive character, it is likely that the structure of soot BC; therefore, its interactions in the environment are complex and it is not simply a recalcitrant material.
ContributorsHamilton, George (Author) / Hartnett, Hilairy E (Thesis advisor) / Herckes, Pierre (Committee member) / Hall, Sharon (Committee member) / Arizona State University (Publisher)
Created2013
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Description

Hydrology and biogeochemistry are coupled in all systems. However, human decision-making regarding hydrology and biogeochemistry are often separate, even though decisions about hydrologic systems may have substantial impacts on biogeochemical patterns and processes. The overarching question of this dissertation was: How does hydrologic engineering interact with the effects of nutrient

Hydrology and biogeochemistry are coupled in all systems. However, human decision-making regarding hydrology and biogeochemistry are often separate, even though decisions about hydrologic systems may have substantial impacts on biogeochemical patterns and processes. The overarching question of this dissertation was: How does hydrologic engineering interact with the effects of nutrient loading and climate to drive watershed nutrient yields? I conducted research in two study systems with contrasting spatial and temporal scales. Using a combination of data-mining and modeling approaches, I reconstructed nitrogen and phosphorus budgets for the northeastern US over the 20th century, including anthropogenic nutrient inputs and riverine fluxes, for ~200 watersheds at 5 year time intervals. Infrastructure systems, such as sewers, wastewater treatment plants, and reservoirs, strongly affected the spatial and temporal patterns of nutrient fluxes from northeastern watersheds. At a smaller scale, I investigated the effects of urban stormwater drainage infrastructure on water and nutrient delivery from urban watersheds in Phoenix, AZ. Using a combination of field monitoring and statistical modeling, I tested hypotheses about the importance of hydrologic and biogeochemical control of nutrient delivery. My research suggests that hydrology is the major driver of differences in nutrient fluxes from urban watersheds at the event scale, and that consideration of altered hydrologic networks is critical for understanding anthropogenic impacts on biogeochemical cycles. Overall, I found that human activities affect nutrient transport via multiple pathways. Anthropogenic nutrient additions increase the supply of nutrients available for transport, whereas hydrologic infrastructure controls the delivery of nutrients from watersheds. Incorporating the effects of hydrologic infrastructure is critical for understanding anthropogenic effects on biogeochemical fluxes across spatial and temporal scales.

ContributorsHale, Rebecca Leslie (Author) / Grimm, Nancy (Thesis advisor) / Childers, Daniel (Committee member) / Vivoni, Enrique (Committee member) / York, Abigail (Committee member) / Wu, Jianguo (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients,

Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients, such as iron, copper, and molybdenum. This work investigated the effects of BSC activity on soil solution concentrations of bioessential elements and examined the microbial production of organic chelators, called siderophores. I found that aluminum, vanadium, copper, zinc, and molybdenum were solubilized in the action of crusts, while nickel, zinc, arsenic, and zirconium were immobilized by crust activity. Potassium and manganese displayed behavior consistent with biological removal and mobilization, whereas phosphorus and iron solubility were dominated by abiotic processes. The addition of bioavailable nitrogen altered the effects of BSCs on soil element mobilization. In addition, I found that the biogeochemical activites of BSCs were limited by molybdenum, a fact that likely contributes to co-limitation by nitrogen. I confirmed the presence of siderophore producing microbes in BSCs. Siderophores are low-molecular weight organic compounds that are released by bacteria to increase element solubility and facilitate element uptake; siderophore production is likely the mechanism by which BSCs affect the patterns I observed in soil solution element concentrations. Siderophore producers were distributed across a range of bacterial groups and ecological niches within crusts, suggesting that siderophore production influences the availability of a variety of elements for use in many physiological processes. Four putative siderophore compounds were identified using electrospray ionization mass spectrometry; further attempts to characterize the compounds confirmed two true siderophores. Taken together, the results of my work provide information about micronutrient cycling within crusts that can be applied to BSC conservation and management. Fertilization with certain elements, particularly molybdenum, may prove to be a useful technique to promote BSC growth and development which would help prevent arid land degradation. Furthermore, understanding the effects of BSCs on soil element mobility could be used to develop useful biomarkers for the study of the existence and distribution of crust-like communities on ancient Earth, and perhaps other places, like Mars.
ContributorsNoonan, Kathryn Alexander (Author) / Hartnett, Hilairy (Thesis advisor) / Anbar, Ariel (Committee member) / Garcia-Pichel, Ferran (Committee member) / Shock, Everett (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Despite public demand for climate change mitigation and natural open space conservancy, existing political and design efforts are only beginning to address the declining efficacy of the biotic carbon pool (C-pool) to sequester carbon. Advances in understanding of biogeochemical processes have provided methods for estimating carbon embodied in natural open

Despite public demand for climate change mitigation and natural open space conservancy, existing political and design efforts are only beginning to address the declining efficacy of the biotic carbon pool (C-pool) to sequester carbon. Advances in understanding of biogeochemical processes have provided methods for estimating carbon embodied in natural open spaces and enhancing carbon sequestration efficacy. In this study, the benefits of carbon embodied in dryland open spaces are determined by estimating carbon flux and analyzing ecological, social, and economic benefits provided by sequestered carbon. Understanding the ecological processes and derived benefits of carbon exchange in dryland open spaces will provide insight into enhancing carbon sequestration efficacy. Open space carbon is estimated by calculating the amount of carbon sequestration (estimated in Mg C / ha / y) in dryland open space C-pools. Carbon sequestration in dryland open spaces can be summarized in five open space typologies: hydric, mesic, aridic, biomass for energy agriculture, and traditional agriculture. Hydric (wetland) systems receive a significant amount of moisture; mesic (riparian) systems receive a moderate amount of moisture; and aridic (dry) systems receive low amounts of moisture. Biomass for energy production (perennial biomass) and traditional agriculture (annual / traditional biomass) can be more effective carbon sinks if managed appropriately. Impacts of design interventions to the carbon capacity of dryland open space systems are calculated by estimating carbon exchange in existing open space (base case) compared to projections of carbon sequestered in a modified system (prototype design). A demonstration project at the Lower San Pedro River Watershed highlights the potential for enhancing carbon sequestration. The site-scale demonstration project takes into account a number of limiting factors and opportunities including: availability of water and ability to manipulate its course, existing and potential vegetation, soil types and use of carbon additives, and land-use (particularly agriculture). Specific design challenges to overcome included: restoring perennial water to the Lower San Pedro River, reestablishing hydric and mesic systems, linking fragmented vegetation, and establishing agricultural systems that provide economic opportunities and act as carbon sinks. The prototype design showed enhancing carbon sequestration efficacy by 128-133% is possible with conservative design interventions.
ContributorsHuck, Erick (Author) / Cook, Edward (Thesis advisor) / Green, Douglas (Committee member) / Brooks, Kenneth (Committee member) / Montemayor, Gabriel (Committee member) / Arizona State University (Publisher)
Created2012
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Under current climate conditions northern peatlands mostly act as C sinks; however, changes in climate and environmental conditions, can change the soil carbon decomposition cascade, thus altering the sink status. Here I studied one of the most abundant northern peatland types, poor fen, situated along a climate gradient from tundra

Under current climate conditions northern peatlands mostly act as C sinks; however, changes in climate and environmental conditions, can change the soil carbon decomposition cascade, thus altering the sink status. Here I studied one of the most abundant northern peatland types, poor fen, situated along a climate gradient from tundra (Daring Lake, Canada) to boreal forest (Lutose, Canada) to temperate broadleaf and mixed forest (Bog Lake, MN and Chicago Bog, NY) biomes to assess patterns of microbial abundance across the climate gradient. Principal component regression analysis of the microbial community and environmental variables determined that mean annual temperature (MAT) (r2=0.85), mean annual precipitation (MAP) (r2=0.88), and soil temperature (r2=0.77), were the top significant drivers of microbial community composition (p < 0.001). Niche breadth analysis revealed the relative abundance of Intrasporangiaceae, Methanobacteriaceae and Candidatus Methanoflorentaceae fam. nov. to increase when MAT and MAP decrease. The same analysis showed Spirochaetaceae, Methanosaetaceae and Methanoregulaceae to increase in relative abundance when MAP, soil temperature and MAT increased, respectively. These findings indicated that climate variables were the strongest predictors of microbial community composition and that certain taxa, especially methanogenic families demonstrate distinct patterns across the climate gradient. To evaluate microbial production of methanogenic substrates, I carried out High Resolution-DNA-Stable Isotope Probing (HR-DNA-SIP) to evaluate the active portion of the community’s intermediary ecosystem metabolic processes. HR-DNA-SIP revealed several challenges in efficiency of labelling and statistical identification of responders, however families like Veillonellaceae, Magnetospirillaceae, Acidobacteriaceae 1, were found ubiquitously active in glucose amended incubations. Differences in metabolic byproducts from glucose amendments show distinct patterns in acetate and propionate accumulation across sites. Families like Spirochaetaceae and Sphingomonadaceae were only found to be active in select sites of propionate amended incubations. By-product analysis from propionate incubations indicate that the northernmost sites were acetate-accumulating communities. These results indicate that microbial communities found in poor fen northern peatlands are strongly influenced by climate variables predicted to change under current climate scenarios. I have identified patterns of relative abundance and activity of select microbial taxa, indicating the potential for climate variables to influence the metabolic pathway in which carbon moves through peatland systems.
ContributorsSarno, Analissa Flores (Author) / Cadillo-Quiroz, Hinsby (Thesis advisor) / Garcia-Pichel, Ferran (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Childers, Daniel (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Two challenges in the implementation of enzyme induced carbonate precipitation(EICP) are the cost of enzyme and the variability of the enzyme. Urease enzyme costs can be lowered drastically with the use of crude extract from plant materials, but experience has shown variability in the source of the crude urease enzyme, the crude urease

Two challenges in the implementation of enzyme induced carbonate precipitation(EICP) are the cost of enzyme and the variability of the enzyme. Urease enzyme costs can be lowered drastically with the use of crude extract from plant materials, but experience has shown variability in the source of the crude urease enzyme, the crude urease enzyme extraction methods, and the concentration of the EICP solution can cause significant variability in the efficacy of the EICP solution. This thesis examines the variability in the efficacy of crude enzyme derived from jack beans (Canavalia ensiformis) and sword beans (Canavalia gladiata), two of the most commonly used sources of urease enzyme for EICP. The sources of variability investigated herein include the crude extraction method (including the effect of the bean husks on extraction) and different chemical constituent concentrations. These effects were assessed using enzyme activity measurements and precipitation efficiency tests. The activity tests were performed via spectrophotometry using Nessler's reagent. The precipitation tests looked at the influence of chemical constituent concentrations of 0.67 M calcium chloride and 1 M urea with non-fat dry milk in the EICP solutions and a higher concentration solution with chemical constituent concentrations of 2 M for both calcium chloride and urea with non-fat dry milk. The high concentration solution was selected based on preliminary testing results to maximize carbonate precipitation in one cycle of treatment. Significant sources of a decline in activity (and increase in variation) of the crude urease enzyme were found in extraction from sword beans with husks, high chemical constituent concentrations, and juicing instead of cheesecloth filtration. This thesis also examines the accuracy of commonly used correlation factors for converting electrical conductivity to urease enzyme activity. Crude jack bean and sword bean urease enzyme activity measurement via electrical conductivity was found to have a correlation coefficient that differed from the previously reported correlation when compared to activity measured via the more accurate spectrophotometry using Nessler’s reagent measurements.
ContributorsPearson, Rayanna (Author) / Kavazanjian, Edward (Thesis advisor) / Khodadadi Tirkolaei, Hamed (Committee member) / Salifu, Emmanuel (Committee member) / Arizona State University (Publisher)
Created2022
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Trichloroethene (TCE) and hexavalent chromium (Cr (VI)) are ubiquitous subsurface contaminants affecting the water quality and threatening human health. Microorganisms capable of TCE and Cr (VI) reductions can be explored for bioremediation at contaminated sites. The goal of my dissertation research was to address challenges that decrease the

Trichloroethene (TCE) and hexavalent chromium (Cr (VI)) are ubiquitous subsurface contaminants affecting the water quality and threatening human health. Microorganisms capable of TCE and Cr (VI) reductions can be explored for bioremediation at contaminated sites. The goal of my dissertation research was to address challenges that decrease the efficiency of bioremediation in the subsurface. Specifically, I investigated strategies to (i) promote improve microbial reductive dechlorination extent through the addition of Fe0 and (ii) Cr (VI) bio-reduction through enrichment of specialized microbial consortia. Fe0 can enhance microbial TCE reduction by inducing anoxic conditions and generating H2 (electron donor). I first evaluated the effect of Fe0 on microbial reduction of TCE (with ClO4– as co-contaminant) using semi-batch soil microcosms. Results showed that high concentration of Fe0 expected during in situ remediation inhibited microbial TCE and ClO4– reduction when added together with Dehalococcoides mccartyi-containing cultures. A low concentration of aged Fe0 enhanced microbial TCE dechlorination to ethene and supported complete microbial ClO4– reduction. I then evaluated a decoupled Fe0 and biostimulation/bioaugmentation treatment approach using soil packed columns with continuous flow of groundwater. I demonstrated that microbial TCE reductive dechlorination to ethene can be benefitted by Fe0 abiotic reactions, when biostimulation and bioaugmentation are performed downstream of Fe0 addition. Furthermore, I showed that ethene production can be sustained in the presence of aerobic groundwater (after Fe0 exhaustion) by the addition of organic substrates. I hypothesized that some lessons learned from TCE Bioremediation can be applied also for other pollutants that can benefit from anaerobic reductions, like Cr (VI). Bioremediation of Cr (VI) has historically relied on biostimulation of native microbial communities, partially due to the lack of knowledge of the benefits of adding enriched consortia of specialized microorganisms (bioaugmentation). To determine the merits of a specialized consortium on bio-reduction of Cr (VI), I first enriched a culture on lactate and Cr (VI). The culture had high abundance of putative Morganella species and showed rapid and sustained Cr (VI) bio-reduction compared to a subculture grown with lactate only (without Morganella). Overall, this dissertation work documents possible strategies for synergistic abiotic and biotic chlorinated ethenes reduction, and highlights that specialized consortia may benefit Cr (VI) bio-reduction.
ContributorsMohana Rangan, Srivatsan (Author) / Krajmalnik-Brown, Rosa (Thesis advisor) / Delgado, Anca G (Thesis advisor) / Torres, César I (Committee member) / van Paassen, Leon (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) are crucial nutrients for autotrophic and heterotrophic microbial life, respectively, in hydrothermal systems. Biogeochemical processes that control amounts of DIC and DOC in Yellowstone hot springs can be investigated by measuring carbon abundances and respective isotopic values. A decade and a

Dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) are crucial nutrients for autotrophic and heterotrophic microbial life, respectively, in hydrothermal systems. Biogeochemical processes that control amounts of DIC and DOC in Yellowstone hot springs can be investigated by measuring carbon abundances and respective isotopic values. A decade and a half of field work in 10 regions within Yellowstone National Park and subsequent geochemical lab analyses reveal that sulfate-dominant acidic regions have high DOC (Up to 57 ppm C) and lower DIC (up to 50 ppm C) compared to neutral-chloride regions with low DOC (< 2 ppm C) and higher DIC (up to 100 ppm C). Abundances and isotopic data suggest that sedimentary rock erosion by acidic hydrothermal fluids, fresh snow-derived meteoric water, and exogenous carbon input allowed by local topography may affect DOC levels. Evaluating the isotopic compositions of DIC and DOC in hydrothermal fluids gives insight on the geology and microbial life in the subsurface between different regions. DIC δ13C values range from -4‰ to +5‰ at pH 5-9 and from -10‰ to +3‰ at pH 2-5 with several springs lower than -10‰. DOC δ13C values parkwide range from -10‰ to -30‰. Within this range, neutral-chloride regions in the Lower Geyser Basin have lighter isotopes than sulfate-dominant acidic regions. In hot springs with elevated levels of DOC, the range only varies between -20‰ and -26‰ which may be caused by local exogenous organic matter runoff. Combining other geochemical measurements, such as differences in chloride and sulfate concentrations, demonstrates that some regions contain mixtures of multiple fluids moving through the complex hydrological system in the subsurface. The mixing of these fluids may account for increased levels of DOC in meteoric sulfate-dominant acidic regions. Ultimately, the foundational values of dissolved carbon and their isotopic composition is provided in a parkwide study, so results can be combined with future studies that apply different sequencing analyses to understand specific biogeochemical cycling and microbial communities that occur in individual hot springs.
ContributorsBarnes, Tanner (Author) / Shock, Everett (Thesis advisor) / Meyer-Dombard, D'Arcy (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2023