This collection includes both ASU Theses and Dissertations, submitted by graduate students, and the Barrett, Honors College theses submitted by undergraduate students. 

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As the use of engineered nanomaterials (ENMs) in consumer products becomes more common, the amount of ENMs entering wastewater treatment plants (WWTPs) increases. Investigating the fate of ENMs in WWTPs is critical for risk assessment and pollution control. The objectives of this dissertation were to (1) quantify and characterize titanium

As the use of engineered nanomaterials (ENMs) in consumer products becomes more common, the amount of ENMs entering wastewater treatment plants (WWTPs) increases. Investigating the fate of ENMs in WWTPs is critical for risk assessment and pollution control. The objectives of this dissertation were to (1) quantify and characterize titanium (Ti) in full-scale wastewater treatment plants, (2) quantify sorption of different ENMs to wastewater biomass in laboratory-scale batch reactors, (3) evaluate the use of a standard, soluble-pollutant sorption test method for quantifying ENM interaction with wastewater biomass, and (4) develop a mechanistic model of a biological wastewater treatment reactor to serve as the basis for modeling nanomaterial fate in WWTPs. Using titanium (Ti) as a model material for the fate of ENMs in WWTPs, Ti concentrations were measured in 10 municipal WWTPs. Ti concentrations in pant influent ranged from 181 to 3000 µg/L, and more than 96% of Ti was removed, with effluent Ti concentrations being less than 25 µg/L. Ti removed from wastewater accumulated in solids at concentrations ranging from 1 to 6 µg Ti/mg solids. Using transmission electron microscopy, spherical titanium oxide nanoparticles with diameters ranging from 4 to 30 nm were found in WWTP effluents, evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems. Batch experiments were conducted to quantify sorption of different ENM types to activated sludge. Percentages of sorption to 400 mg TSS/L biomass ranged from about 10 to 90%, depending on the ENM material and functionalization. Natural organic matter, surfactants, and proteins had a stabilizing effect on most of the ENMs tested. The United States Environmental Protection Agency's standard sorption testing method (OPPTS 835.1110) used for soluble compounds was found to be inapplicable to ENMs, as freeze-dried activated sludge transforms ENMs into stable particles in suspension. In conjunction with experiments, we created a mechanistic model of the microbiological processes in membrane bioreactors to predict MBR, extended and modified this model to predict the fate of soluble micropollutants, and then discussed how the micropollutant fate model could be used to predict the fate of nanomaterials in wastewater treatment plants.
ContributorsKiser, Mehlika Ayla (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Hristovski, Kiril D (Committee member) / Arizona State University (Publisher)
Created2011
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Description
On average, our society generates ~0.5 ton of municipal solid waste per person annually. Biomass waste can be gasified to generate synthesis gas (syngas), a gas mixture consisting predominantly of CO, CO2, and H2. Syngas, rich in carbon and electrons, can fuel the metabolism of carboxidotrophs, anaerobic microorganisms that

On average, our society generates ~0.5 ton of municipal solid waste per person annually. Biomass waste can be gasified to generate synthesis gas (syngas), a gas mixture consisting predominantly of CO, CO2, and H2. Syngas, rich in carbon and electrons, can fuel the metabolism of carboxidotrophs, anaerobic microorganisms that metabolize CO (a toxic pollutant) and produce biofuels (H2, ethanol) and commodity chemicals (acetate and other fatty acids). Despite the attempts for commercialization of syngas fermentation by several companies, the metabolic processes involved in CO and syngas metabolism are not well understood. This dissertation aims to contribute to the understanding of CO and syngas fermentation by uncovering key microorganisms and understanding their metabolism. For this, microbiology and molecular biology techniques were combined with analytical chemistry analyses and deep sequencing techniques. First, environments where CO is commonly detected, including the seafloor, volcanic sand, and sewage sludge, were explored to identify potential carboxidotrophs. Since carboxidotrophs from sludge consumed CO 1000 faster than those in nature, mesophilic sludge was used as inoculum to enrich for CO- and syngas- metabolizing microbes. Two carboxidotrophs were isolated from this culture: an acetate/ethanol-producer 99% phylogenetically similar to Acetobacterium wieringae and a novel H2-producer, Pleomorphomonas carboxidotrophicus sp. nov. Comparison of CO and syngas fermentation by the CO-enriched culture and the isolates suggested mixed-culture syngas fermentation as a better alternative to ferment CO-rich gases. Advantages of mixed cultures included complete consumption of H2 and CO2 (along with CO), flexibility under different syngas compositions, functional redundancy (for acetate production) and high ethanol production after providing a continuous supply of electrons. Lastly, dilute ethanol solutions, typical of syngas fermentation processes, were upgraded to medium-chain fatty acids (MCFA), biofuel precursors, through the continuous addition of CO. In these bioreactors, methanogens were inhibited and Peptostreptococcaceae and Lachnospiraceae spp. most likely partnered with carboxidotrophs for MCFA production. These results reveal novel microorganisms capable of effectively consuming an atmospheric pollutant, shed light on the interplay between syngas components, microbial communities, and metabolites produced, and support mixed-culture syngas fermentation for the production of a wide variety of biofuels and commodity chemicals.
ContributorsEsquivel Elizondo, Sofia Victoria (Author) / Krajmalnik-Brown, Rosa (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Delgado, Anca G. (Committee member) / Torres, Cesar I. (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1) establishing NP detecting methods with high sensitivity to tackle low concentration and small sizes, (2) achieving assays capable of measuring

Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1) establishing NP detecting methods with high sensitivity to tackle low concentration and small sizes, (2) achieving assays capable of measuring NP surface reactivity and identifying surface reaction mechanisms, and (3) understanding the impact of surface adsorption of ions on surface reactivity of NPs in water.

The size detection limit of single particle inductively coupled plasma spectrometry (spICP-MS) was determined for 40 elements, demonstrating the feasibility of spICP-MS to different NP species in water. The K-means Clustering Algorithm was used to process the spICP-MS signals, and achieved precise particle-noise differentiation and quantitative particle size resolution. A dry powder assay based on NP-catalyzed methylene blue (MB) reduction was developed to rapidly and sensitively detect metallic NPs in water by measuring their catalytic reactivity.

Four different wet-chemical-based NP surface reactivity assays were demonstrated: “borohydride reducing methylene blue (BHMB)”, “ferric reducing ability of nanoparticles (FRAN)”, “electron paramagnetic resonance detection of hydroxyl radical (EPR)”, and “UV-illuminated methylene blue degradation (UVMB)”. They gave different reactivity ranking among five NP species, because they targeted for different surface reactivity types (catalytic, redox and photo reactivity) via different reaction mechanisms. Kinetic modeling frameworks on the assay outcomes revealed two surface electron transfer schemes, namely the “sacrificial reducing” and the “electrode discharging”, and separated interfering side reactions from the intended surface reaction.

The application of NPs in chemical mechanical polishing (CMP) was investigated as an industrial case to understand NP surface transformation via adsorbing ions in water. Simulation of wastewater treatment showed CMP NPs were effectively removed (>90%) by lime softening at high pH and high calcium dosage, but 20-40% of them remained in water after biomass adsorption process. III/V ions (InIII, GaIII, and AsIII/V) derived from semiconductor materials showed adsorption potentials to common CMP NPs (SiO2, CeO2 and Al2O3), and a surface complexation model was developed to determine their intrinsic complexation constants for different NP species. The adsorption of AsIII and AsV ions onto CeO2 NPs mitigated the surface reactivity of CeO2 NPs suggested by the FRAN and EPR assays. The impact of the ion adsorption on the surface reactivity of CeO2 NPs was related to the redox state of Ce and As on the surface, but varied with ion species and surface reaction mechanisms.
ContributorsBi, Xiangyu (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Herckes, Pierre (Committee member) / Richert, Ranko (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Widespread use of chlorinated solvents for commercial and industrial purposes makes co-occurring contamination by 1,1,1-trichloroethane (TCA), trichloroethene (TCE), and 1,4-dioxane (1,4-D) a serious problem for groundwater. TCE and TCA often are treated by reductive dechlorination, while 1,4-D resists reductive treatment. Aerobic bacteria are able to oxidize 1,4-D, but

Widespread use of chlorinated solvents for commercial and industrial purposes makes co-occurring contamination by 1,1,1-trichloroethane (TCA), trichloroethene (TCE), and 1,4-dioxane (1,4-D) a serious problem for groundwater. TCE and TCA often are treated by reductive dechlorination, while 1,4-D resists reductive treatment. Aerobic bacteria are able to oxidize 1,4-D, but the biological oxidation of 1,4-D could be inhibited TCA, TCE, and their reductive transformation products. To overcome the challenges from co-occurring contamination, I propose a two-stage synergistic system. First, anaerobic reduction of the chlorinated hydrocarbons takes place in a H2-based hollow-fiber “X-film” (biofilm or catalyst-coated film) reactor (MXfR), where “X-film” can be a “bio-film” (MBfR) or an abiotic “palladium-film” (MPfR). Then, aerobic removal of 1,4-D and other organic compounds takes place in an O2-based MBfR. For the reductive part, I tested reductive bio-dechlorination of TCA and TCE simultaneously in an MBfR. I found that the community of anaerobic bacteria can rapidly reduce TCE to cis-dichloroethene (cis-DCE), but further reductions of cis-DCE to vinyl chloride (VC) and VC to ethene were inhibited by TCA. Also, it took months to grow a strong biofilm that could reduce TCA and TCE. Another problem with reductive dechlorination in the MBfR is that mono-chloroethane (MCA) was not reduced to ethane. In contrast, a film of palladium nano-particles (PdNPs), i.e., an MPfR, could the simultaneous reductions of TCA and TCE to mainly ethane, with only small amounts of intermediates: 1,1-dichloroethane (DCA) (~3% of total influent TCA and TCE) and MCA (~1%) in continuous operation. For aerobic oxidation, I enriched an ethanotrophic culture that could oxidize 1,4-D with ethane as the primary electron donor. An O2-based MBfR, inoculated with the enriched ethanotrophic culture, achieved over 99% 1,4-D removal with ethane as the primary electron donor in continuous operation. Finally, I evaluated two-stage treatment with a H2-based MPfR followed by an O2-MBfR. The two-stage system gave complete removal of TCA, TCE, and 1,4-D in continuous operation.
ContributorsLuo, Yihao (Author) / Rittmann, Bruce E. (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Zhou, Chen (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Microbial electrochemical cells (MXCs) serve as an alternative anaerobic technology to anaerobic digestion for efficient energy recovery from high-strength organic wastes such as primary sludge (PS). The overarching goal of my research was to address energy conversion from PS to useful resources (e.g. hydrogen or hydrogen peroxide) through bio-

Microbial electrochemical cells (MXCs) serve as an alternative anaerobic technology to anaerobic digestion for efficient energy recovery from high-strength organic wastes such as primary sludge (PS). The overarching goal of my research was to address energy conversion from PS to useful resources (e.g. hydrogen or hydrogen peroxide) through bio- and electro-chemical anaerobic conversion processes in MXCs.

First, a new flat-pate microbial electrolysis cell (MEC) was designed with high surface area anodes using carbon fibers, but without creating a large distance between the anode and the cathode (<0.5 cm) to reduce Ohmic overpotential. Through the improved design, operation, and electrochemical characterization, the applied voltages were reduced from 1.1 to ~0.85 V, at 10 A m-2. Second, PS conversion was examined through hydrolysis, fermentation, methanogenesis, and/or anode respiration. Since pretreatment often is required to accelerate hydrolysis of organic solids, I evaluated pulsed electric field technology on PS showing a modest improvement of energy conversion through methanogenesis and fermentation, as compared to the conversion from waste activated sludge (WAS) or WAS+PS. Then, a two-stage system (prefermented PS-fed MEC) yielded successful performance in terms of Coulombic efficiency (95%), Coulombic recovery (CR, 80%), and COD-removal efficiency (85%). However, overall PS conversion to electrical current (or CR) through pre-fermentation and MEC, was just ~16%. Next, a single-stage system (direct PS-fed MEC) with semi-continuous operation showed 34% CR at a 9-day hydraulic retention time. The PS-fed MEC also showed an important pH dependency, in which high pH (> 8) in the anode chamber improved anode respiration along with methanogen inhibition. Finally, H2O2 was produced in a PS-fed microbial electrochemical cell with a low energy requirement (~0.87 kWh per kg H2O2). These research developments will provide groundbreaking knowledge for MXC design, commercial application, and anaerobic energy conversion from other high-strength organic wastes to resources.
ContributorsKi, Dong Won (Author) / Torres, César I (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Parameswaran, Prathap (Committee member) / Popat, Sudeep C (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The finite supply of current energy production materials has created opportunities for the investigation of alternative energy sources in many fields. One example is the use of microorganisms in bioenergy applications, such as microbial fuel cells. Present in many types of environments, microorganisms with the ability to respire

The finite supply of current energy production materials has created opportunities for the investigation of alternative energy sources in many fields. One example is the use of microorganisms in bioenergy applications, such as microbial fuel cells. Present in many types of environments, microorganisms with the ability to respire solid electron acceptors have become of increasing relevance to alternative energy and wastewater treatment research. In this dissertation, several aspects of anode respiration are investigated, with the goal of increasing the limited understanding of the mechanisms of electron transport through the use of advanced electrochemical methods. Biofilms of Geobacter sulfurreducens, the model anode respiring organism, as well as its alkaliphilic relative, Geoalkalibacter ferrihydriticus, were investigated using chronoamperometry, electrochemical impedance spectroscopy, and cyclic voltammetry.

In G. sulfurreducens, two distinct pathways of electron transport were observed through the application of advanced electrochemical techniques on anode biofilms in microbial electrochemical cells. These pathways were found to be preferentially expressed, based on the poised anode potential (redox potential) of the electrode. In Glk. ferrihydriticus, four pathways for electron transport were found, showing an even greater diversity in electron transport pathway utilization as compared to G. sulfurreducens. These observations provide insights into the diversity of electron transport pathways present in anode-respiring bacteria and introduce the necessity of further characterization for pathway identification.

Essential to science today, communication of pressing scientific issues to the lay audience may present certain difficulties. This can be seen especially with the topics that are considered socio-scientific issues, those considered controversial in society but not for scientists. This dissertation explores the presentation of alternative and renewable energy technologies and climate change in undergraduate education. In introductory-level Biology, Chemistry, and Physics textbooks, the content and terminology presented were analyzed for individual textbooks and used to evaluate discipline-based trends. Additional extensions were made between teaching climate change with the active learning technique of citizen science using past research gains from studies of evolution. These observations reveal patterns in textbook content for energy technologies and climate change, as well as exploring new aspects of teaching techniques.
ContributorsYoho, Rachel Ann (Author) / Torres, César I (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Popat, Sudeep C (Committee member) / Vanmali, Binaben H (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The application of microalgal biofilms in wastewater treatment has great advantages such as abolishing the need for energy intensive aerators and recovering nutrients as energy, thus reducing the energy requirement of wastewater treatment several-fold. A 162 cm2 algal biofilm reactor with good wastewater treatment performance and a regular harvesting procedure

The application of microalgal biofilms in wastewater treatment has great advantages such as abolishing the need for energy intensive aerators and recovering nutrients as energy, thus reducing the energy requirement of wastewater treatment several-fold. A 162 cm2 algal biofilm reactor with good wastewater treatment performance and a regular harvesting procedure was studied at lab scale to gain an understanding of effectual parameters such as hydraulic retention time (HRT; 2.6 and 1.3 hrs), liquid level (LL; 0.5 and 1.0 cm), and solids retention time (SRT; 3 and 1.5 wks). A revised synthetic wastewater “Syntho 3.7” was used as a surrogate of domestic primary effluent for nutrient concentration consistency in the feed lines. In the base case (2.6 hr HRT, 0.5 cm LL, and 3 wk SRT), percent removals of 69 ± 2 for total nitrogen (TN), 54 ± 21 for total phosphorous (TP), and 60 ± 7 for chemical oxygen demand (COD) were achieved and 4.0 ± 1.6 g/m2/d dry biomass was produced. A diffusion limitation was encountered when increasing the liquid level, while the potential to further decrease the HRT remains. Nonlinear growth kinetics was observed in comparing SRT variations, and promoting autotrophic growth seems possible. Future work will look towards producing a mathematical model and further testing the aptness of this system for large-scale implementation.
ContributorsHalloum, Ibrahim (Author) / Torres, César I (Thesis advisor) / Popat, Sudeep C (Committee member) / Rittmann, Bruce E. (Committee member) / Arizona State University (Publisher)
Created2016
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Description
ABSTRACT

Sustainable global energy production is one of the grand challenges of the 21st century. Next-generation renewable energy sources include using photosynthetic microbes such as cyanobacteria for efficient production of sustainable fuels from sunlight. The cyanobacterium Synechocystis PCC 6803 (Synechocystis) is a genetically tractable model organism for plant-like photosynthesis that is

ABSTRACT

Sustainable global energy production is one of the grand challenges of the 21st century. Next-generation renewable energy sources include using photosynthetic microbes such as cyanobacteria for efficient production of sustainable fuels from sunlight. The cyanobacterium Synechocystis PCC 6803 (Synechocystis) is a genetically tractable model organism for plant-like photosynthesis that is used to develop microbial biofuel technologies. However, outside of photosynthetic processes, relatively little is known about the biology of microbial phototrophs such as Synechocystis, which impairs their development into market-ready technologies. My research objective was to characterize strategic aspects of Synechocystis biology related to its use in biofuel production; specifically, how the cell surface modulates the interactions between Synechocystis cells and the environment. First, I documented extensive biofouling, or unwanted biofilm formation, in a 4,000-liter roof-top photobioreactor (PBR) used to cultivate Synechocystis, and correlated this cell-binding phenotype with changes in nutrient status by developing a bench-scale assay for axenic phototrophic biofilm formation. Second, I created a library of mutants that lack cell surface structures, and used this biofilm assay to show that mutants lacking the structures pili or S-layer have a non-biofouling phenotype. Third, I analyzed the transcriptomes of cultures showing aggregation, another cell-binding phenotype, and demonstrated that the cells were undergoing stringent response, a type of conserved stress response. Finally, I used contaminant Consortia and statistical modeling to test whether Synechocystis mutants lacking cell surface structures could reduce contaminant growth in mixed cultures. In summary, I have identified genetic and environmental means of manipulating Synechocystis strains for customized adhesion phenotypes, for more economical biomass harvesting and non-biofouling methods. Additionally, I developed a modified biofilm assay and demonstrated its utility in closing a key gap in the field of microbiology related to axenic phototrophic biofilm formation assays. Also, I demonstrated that statistical modeling of contaminant Consortia predicts contaminant growth across diverse species. Collectively, these findings serve as the basis for immediately lowering the cost barrier of Synechocystis biofuels via a more economical biomass-dewatering step, and provide new research tools for improving Synechocystis strains and culture ecology management for improved biofuel production.
ContributorsAllen, Rebecca Custer (Author) / Curtiss Iii, Roy (Thesis advisor) / Krajmalnik-Brown, Rosa (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Vermaas, Willem (Committee member) / Arizona State University (Publisher)
Created2016
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Description
Microbial Electrochemical Cell (MXC) technology harnesses the power stored in wastewater by using anode respiring bacteria (ARB) as a biofilm catalyst to convert the energy stored in waste into hydrogen or electricity. ARB, or exoelectrogens, are able to convert the chemical energy stored in wastes into electrical energy by transporting

Microbial Electrochemical Cell (MXC) technology harnesses the power stored in wastewater by using anode respiring bacteria (ARB) as a biofilm catalyst to convert the energy stored in waste into hydrogen or electricity. ARB, or exoelectrogens, are able to convert the chemical energy stored in wastes into electrical energy by transporting electrons extracellularly and then transferring them to an electrode. If MXC technology is to be feasible for ‘real world’ applications, it is essential that diverse ARB are discovered and their unique physiologies elucidated- ones which are capable of consuming a broad spectrum of wastes from different contaminated water sources.

This dissertation examines the use of Gram-positive thermophilic (60 ◦C) ARB in MXCs since very little is known regarding the behavior of these microorganisms in this setting. Here, we begin with the draft sequence of the Thermincola ferriacetica genome and reveal the presence of 35 multiheme c-type cytochromes. In addition, we employ electrochemical techniques including cyclic voltammetry (CV) and chronoamperometry (CA) to gain insight into the presence of multiple pathways for extracellular electron transport (EET) and current production (j) limitations in T. ferriacetica biofilms.

Next, Thermoanaerobacter pseudethanolicus, a fermentative ARB, is investigated for its ability to ferment pentose and hexose sugars prior to using its fermentation products, including acetate and lactate, for current production in an MXC. Using CA, current production is tracked over time with the generation and consumption of fermentation products. Using CV, the midpoint potential (EKA) of the T. pseudethanolicus EET pathway is revealed.



Lastly, a cellulolytic microbial consortium was employed for the purpose ofassessing the feasibility of using thermophilic MXCs for the conversion of solid waste into current production. Here, a highly enriched consortium of bacteria, predominately from the Firmicutes phylum, is capable of generating current from solid cellulosic materials.
ContributorsLusk, Bradley (Author) / Torres, César I (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Eighty-two percent of the United States population reside in urban areas. The centralized treatment of the municipal wastewater produced by this population is a huge energy expenditure, up to three percent of the entire energy budget of the country. A portion of this energy is able to be recovered

Eighty-two percent of the United States population reside in urban areas. The centralized treatment of the municipal wastewater produced by this population is a huge energy expenditure, up to three percent of the entire energy budget of the country. A portion of this energy is able to be recovered through the process of anaerobic sludge digestion. Typically, this technology converts the solids separated and generated during the wastewater treatment process into methane, a combustible gas that may be burned to generate electricity. Designing and optimizing anaerobic digestion systems requires the measurement of degradation rates for waste-specific kinetic parameters. In this work, I discuss the ways these kinetic parameters are typically measured. I recommend and demonstrate improvements to these commonly used measuring techniques. I provide experimental results of batch kinetic experiments exploring the effect of sludge pretreatment, a process designed to facilitate rapid breakdown of recalcitrant solids, on energy recovery rates. I explore the use of microbial electrochemical cells, an alternative energy recovery technology able to produce electricity directly from sludge digestion, as precise reporters of degradation kinetics. Finally, I examine a fundamental kinetic limitation of microbial electrochemical cells, acidification of the anode respiring biofilm, to improve their performance as kinetic sensors or energy recovery technologies.
ContributorsHart, Steven Gregg (Author) / Torres, César I (Thesis advisor) / Parameswaran, Prathap (Committee member) / Rittmann, Bruce E. (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2020