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Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts,

Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical

Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical formed during ozonation, however estimating the ozone demand of wastewater effluent is complicated due to the presence of reduced inorganic species. A method was developed to estimate ozone consumption only by dissolved organic compounds and predict trace organic oxidation across multiple wastewater sources. Organic and engineered nanomaterial (ENM) CEC removal in constructed wetlands was investigated using batch experiments and continuous-flow microcosms containing decaying wetland plants. CEC removal varied depending on their physico-chemical properties, hydraulic residence time (HRT) and relative quantities of plant materials in the microcosms. At comparable HRTs, ENM removal improved with higher quantity of plant materials due to enhanced sorption which was verified in batch-scale studies with plant materials. A fate-predictive model was developed to evaluate the role of design loading rates on organic CEC removal. Areal removal rates increased with hydraulic loading rates (HLRs) and carbon loading rates (CLRs) unless photolysis was the dominant removal mechanism (e.g. atrazine). To optimize CEC removal, wetlands with different CLRs can be used in combination without lowering the net HLR. Organic CEC removal in denitrifying conditions of constructed wetlands was investigated and selected CECs (e.g. estradiol) were found to biotransform while denitrification occurred. Although level of denitrification was affected by HRT, similar impact on estradiol was not observed due to a dominant effect from plant biomass quantity. Overall, both modeling and experimental findings suggest considering CLR as an equally important factor with HRT or HLR to design constructed wetlands for CEC removal. This dissertation provided directions to select design parameters for ozonation (ozone dose) and constructed wetlands (design loading rates) to meet organic CEC removal goals. Future research is needed to understand fate of ENMs during ozonation and quantify the contributions from different transformation mechanisms occurring in the wetlands to incorporate in a model and evaluate the effect of wetland design.
ContributorsSharif, Fariya (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Fox, Peter (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The influence of climate variability and reclaimed wastewater on the water supply necessitates improved understanding of the treatability of trace and bulk organic matter. Dissolved organic matter (DOM) mobilized during extreme weather events and in treated wastewater includes natural organic matter (NOM), contaminants of emerging concern (CECs), and microbial extracellular

The influence of climate variability and reclaimed wastewater on the water supply necessitates improved understanding of the treatability of trace and bulk organic matter. Dissolved organic matter (DOM) mobilized during extreme weather events and in treated wastewater includes natural organic matter (NOM), contaminants of emerging concern (CECs), and microbial extracellular polymeric substances (EPS). The goal of my dissertation was to quantify the impacts of extreme weather events on DOM in surface water and downstream treatment processes, and to improve membrane filtration efficiency and CECs oxidation efficiency during water reclamation with ozone. Surface water quality, air quality and hydrologic flow rate data were used to quantify changes in DOM and turbidity following dust storms, flooding, or runoff from wildfire burn areas in central Arizona. The subsequent impacts to treatment processes and public perception of water quality were also discussed. Findings showed a correlation between dust storm events and change in surface water turbidity (R2=0.6), attenuation of increased DOM through reservoir systems, a 30-40% increase in organic carbon and a 120-600% increase in turbidity following severe flooding, and differing impacts of upland and lowland wildfires. The use of ozone to reduce membrane fouling caused by vesicles (a subcomponent of EPS) and oxidize CECs through increased hydroxyl radical (HO●) production was investigated. An "ozone dose threshold" was observed above which addition of hydrogen peroxide increased HO● production; indicating the presence of ambient promoters in wastewater. Ozonation of CECs in secondary effluent over titanium dioxide or activated carbon did not increase radial production. Vesicles fouled ultrafiltration membranes faster (20 times greater flux decline) than polysaccharides, fatty acids, or NOM. Based upon the estimated carbon distribution of secondary effluent, vesicles could be responsible for 20-60% of fouling during ultrafiltration and may play a vital role in other environmental processes as well. Ozone reduced vesicle-caused membrane fouling that, in conjunction with the presence of ambient promoters, helps to explain why low ozone dosages improve membrane flux during full-scale water reclamation.
ContributorsBarry, Michelle (Author) / Barry, Michelle C (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Arsenic (As) and chromium (Cr) occur naturally in AZ surface and groundwaters, pose different health impacts, and exhibit different treatment efficacies. Hexavalent chromium (Cr(VI)) has newly recognized human health concerns, and State and Federal agencies are evaluating a low Cr(VI)-specific maximum contaminant level (MCL) for drinking water. Occurrence of Cr

Arsenic (As) and chromium (Cr) occur naturally in AZ surface and groundwaters, pose different health impacts, and exhibit different treatment efficacies. Hexavalent chromium (Cr(VI)) has newly recognized human health concerns, and State and Federal agencies are evaluating a low Cr(VI)-specific maximum contaminant level (MCL) for drinking water. Occurrence of Cr and As in municipal drinking waters and industrial cooling tower waters was quantified by grab samples and compared with sampling results obtained from a new passive sampler developed specifically for Cr(VI). Cr(VI) and As concentrations in groundwater used for cooling tower make-up water concentrations were ~3 ppb and ~4 ppb, respectively, and were concentrated significantly in blowdown water (~20 ppb and ~40 ppb). Based upon pending Cr(VI), As, and other metal regulations, these blowdown waters will need routine monitoring and treatment. Cr(VI) concentrations in a water treatment plant (WTP) raw and finished water samples varied from 0.5 and 2 ppb for grab samples collected every 4 hours for 7 consecutive days using an ISCO sampler. The development of an ion exchange (IX) based passive sampler was validated in the field at the WTP and yielded an average exposure within 1 standard deviation of ISCO sampler grab data. Sampling at both the WTP and cooling towers suggested sources of Cr(III) from treatment chemicals or wood preservatives may exist. Since both facilities use chlorine oxidants, I quantified the apparent (pH=5) second-order rate constant for aqueous chlorine (HOCl/OCl-) with Cr(III) to form Cr(VI) as 0.7 M-1s-1. Under typical conditions (2 ppb Cr(III) ; 2 mg/L Cl2) the half-life for the conversion of Cr(III) to the more toxic form Cr(VI) is 4.7 hours. The occurrence studies in AZ and CA show the Cr(VI) and As treatment of groundwaters will be required to meet stringent Cr(VI) regulations. IX technologies, both strong base anion (SBA) and weak base anion (WBA) resin types were screened (and compared) for Cr removal. The SBA IX process for As removal was optimized by utilizing a reactive iron coagulation and filtration (RCF) process to treat spent IX brine, which was then reused to for SBA resin regeneration.
ContributorsBowen, Alexandra (Author) / Paul, Westerhoff K. (Thesis advisor) / Hristovski, Kiril (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2014
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Description
ABSTRACT &eacutetudes; written for violin ensemble, which include violin duets, trios, and quartets, are less numerous than solo &eacutetudes.; These works rarely go by the title "&eacutetude;," and have not been the focus of much scholarly research. Ensemble &eacutetudes; have much to offer students, teachers and

ABSTRACT &eacutetudes; written for violin ensemble, which include violin duets, trios, and quartets, are less numerous than solo &eacutetudes.; These works rarely go by the title "&eacutetude;," and have not been the focus of much scholarly research. Ensemble &eacutetudes; have much to offer students, teachers and composers, however, because they add an extra dimension to the learning, teaching, and composing processes. This document establishes the value of ensemble &eacutetudes; in pedagogy and explores applications of the repertoire currently available. Rather than focus on violin duets, the most common form of ensemble &eacutetude;, it mainly considers works for three and four violins without accompaniment. Concentrating on the pedagogical possibilities of studying &eacutetudes; in a group, this document introduces creative ways that works for violin ensemble can be used as both &eacutetudes; and performance pieces. The first two chapters explore the history and philosophy of the violin &eacutetude; and multiple-violin works, the practice of arranging of solo &eacutetudes; for multiple instruments, and the benefits of group learning and cooperative learning that distinguish ensemble &eacutetude; study from solo &eacutetude; study. The third chapter is an annotated survey of works for three and four violins without accompaniment, and serves as a pedagogical guide to some of the available repertoire. Representing a wide variety of styles, techniques and levels, it illuminates an historical association between violin ensemble works and pedagogy. The fourth chapter presents an original composition by the author, titled Variations on a Scottish Folk Song: &eacutetude; for Four Violins, with an explanation of the process and techniques used to create this ensemble &eacutetude.; This work is an example of the musical and technical integration essential to &eacutetude; study, and demonstrates various compositional traits that promote cooperative learning. Ensemble &eacutetudes; are valuable pedagogical tools that deserve wider exposure. It is my hope that the information and ideas about ensemble &eacutetudes; in this paper and the individual descriptions of the works presented will increase interest in and application of violin trios and quartets at the university level.
ContributorsLundell, Eva Rachel (Contributor) / Swartz, Jonathan (Thesis advisor) / Rockmaker, Jody (Committee member) / Buck, Nancy (Committee member) / Koonce, Frank (Committee member) / Norton, Kay (Committee member) / Arizona State University (Publisher)
Created2011
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Description
This study examined attitudes and perspectives of classroom guitar students toward the reading of staff notation in music. The purpose of this qualitative research was to reveal these perceptions in the student's own words, and compare them to those of orchestra and band students of comparable experience. Forty-seven students from

This study examined attitudes and perspectives of classroom guitar students toward the reading of staff notation in music. The purpose of this qualitative research was to reveal these perceptions in the student's own words, and compare them to those of orchestra and band students of comparable experience. Forty-seven students from four suburban middle and high schools on the east coast were selected through purposeful sampling techniques. Research instruments included a Musical Background Questionnaire and a thirty-five question Student Survey. Follow-up interviews were conducted with students to clarify or expound upon collected data. Guitar, orchestra, and band teachers were interviewed in order to provide their perspectives on the issues discussed. The Student Survey featured a five-point Likert-type scale, which measured how much students agreed or disagreed with various statements pertaining to their feelings about music, note-reading, or their class at school. Collected data were coded and used to calculate mean scores, standard deviations, and percentages of students in agreement or disagreement with each statement. Interviews were audio recorded and transcribed into a word processing document for analysis. The study found that while a variety of perspectives exist within a typical guitar class, some students do not find note-reading to be necessary for the types of music they desire to learn. Other findings included a perceived lack of relevance toward the classical elements of the guitar programs in the schools, a lack of educational consistency between classroom curricula and private lesson objectives, and the general description of the struggle some guitarists experience with staff notation. Implications of the collected data were discussed, along with recommendations for better engaging these students.
ContributorsWard, Stephen Michael (Author) / Koonce, Frank (Thesis advisor) / Schmidt, Margaret (Thesis advisor) / Buck, Nancy (Committee member) / Rogers, Rodney (Committee member) / McLin, Katherine (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Intimate coupling of Ti2 photocatalysis and biodegradation (ICPB) offers potential for degrading biorecalcitrant and toxic organic compounds much better than possible with conventional wastewater treatments. This study reports on using a novel sponge-type, Ti2-coated biofilm carrier that shows significant adherence of Ti2 to its exterior and the ability to accumulate

Intimate coupling of Ti2 photocatalysis and biodegradation (ICPB) offers potential for degrading biorecalcitrant and toxic organic compounds much better than possible with conventional wastewater treatments. This study reports on using a novel sponge-type, Ti2-coated biofilm carrier that shows significant adherence of Ti2 to its exterior and the ability to accumulate biomass in its interior (protected from UV light and free radicals). First, this carrier was tested for ICPB in a continuous-flow photocatalytic circulating-bed biofilm reactor (PCBBR) to mineralize biorecalcitrant organic: 2,4,5-trichlorophenol (TCP). Four mechanisms possibly acting of ICPB were tested separately: TCP adsorption, UV photolysis/photocatalysis, and biodegradation. The carrier exhibited strong TCP adsorption, while photolysis was negligible. Photocatalysis produced TCP-degradation products that could be mineralized and the strong adsorption of TCP to the carrier enhanced biodegradation by relieving toxicity. Validating the ICPB concept, biofilm was protected inside the carriers from UV light and free radicals. ICPB significantly lowered the diversity of the bacterial community, but five genera known to biodegrade chlorinated phenols were markedly enriched. Secondly, decolorization and mineralization of reactive dyes by ICPB were investigated on a refined Ti2-coated biofilm carrier in a PCBBR. Two typical reactive dyes: Reactive Black 5 (RB5) and Reactive Yellow 86 (RY86), showed similar first-order kinetics when being photocatalytically decolorized at low pH (~4-5), which was inhibited at neutral pH in the presence of phosphate or carbonate buffer, presumably due to electrostatic repulsion from negatively charged surface sites on Ti2, radical scavenging by phosphate or carbonate, or both. In the PCBBR, photocatalysis alone with Ti2-coated carriers could remove RB5 and COD by 97% and 47%, respectively. Addition of biofilm inside macroporous carriers maintained a similar RB5 removal efficiency, but COD removal increased to 65%, which is evidence of ICPB despite the low pH. A proposed ICPB pathway for RB5 suggests that a major intermediate, a naphthol derivative, was responsible for most of the residual COD. Finally, three low-temperature sintering methods, called O, D and DN, were compared based on photocatalytic efficiency and Ti2 adherence. The DN method had the best Ti2-coating properties and was a successful carrier for ICPB of RB5 in a PCBBR.
ContributorsLi, Guozheng (Author) / Rittmann, Bruce E. (Thesis advisor) / Halden, Rolf (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2011
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Description
The overall goal of this dissertation is to advance understanding of biofilm reduction of oxidized contaminants in water and wastewater. Chapter 1 introduces the fundamentals of biological reduction of three oxidized contaminants (nitrate, perchlorate, and trichloriethene (TCE)) using two biofilm processes (hydrogen-based membrane biofilm reactors (MBfR) and packed-bed heterotrophic reactors

The overall goal of this dissertation is to advance understanding of biofilm reduction of oxidized contaminants in water and wastewater. Chapter 1 introduces the fundamentals of biological reduction of three oxidized contaminants (nitrate, perchlorate, and trichloriethene (TCE)) using two biofilm processes (hydrogen-based membrane biofilm reactors (MBfR) and packed-bed heterotrophic reactors (PBHR)), and it identifies the research objectives. Chapters 2 through 6 focus on nitrate removal using the MBfR and PBHR, while chapters 7 through 10 investigate simultaneous reduction of nitrate and another oxidized compound (perchlorate, sulfate, or TCE) in the MBfR. Chapter 11 summarizes the major findings of this research. Chapters 2 and 3 demonstrate nitrate removal in a groundwater and identify the maximum nitrate loadings using a pilot-scale MBfR and a pilot-scale PBHR, respectively. Chapter 4 compares the MBfR and the PBHR for denitrification of the same nitrate-contaminated groundwater. The comparison includes the maximum nitrate loading, the effluent water quality of the denitrification reactors, and the impact of post-treatment on water quality. Chapter 5 theoretically and experimentally demonstrates that the nitrate biomass-carrier surface loading, rather than the traditionally used empty bed contact time or nitrate volumetric loading, is the primary design parameter for heterotrophic denitrification. Chapter 6 constructs a pH-control model to predict pH, alkalinity, and precipitation potential in heterotrophic or hydrogen-based autotrophic denitrification reactors. Chapter 7 develops and uses steady-state permeation tests and a mathematical model to determine the hydrogen-permeation coefficients of three fibers commonly used in the MBfR. The coefficients are then used as inputs for the three models in Chapters 8-10. Chapter 8 develops a multispecies biofilm model for simultaneous reduction of nitrate and perchlorate in the MBfR. The model quantitatively and systematically explains how operating conditions affect nitrate and perchlorate reduction and biomass distribution via four mechanisms. Chapter 9 modifies the nitrate and perchlorate model into a nitrate and sulfate model and uses it to identify operating conditions corresponding to onset of sulfate reduction. Chapter 10 modifies the nitrate and perchlorate model into a nitrate and TCE model and uses it to investigate how operating conditions affect TCE reduction and accumulation of TCE reduction intermediates.
ContributorsTang, Youneng (Author) / Rittmann, Bruce E. (Thesis advisor) / Westerhoff, Paul (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2012
Description
Highly active in the fields of viola performance, composition, recording, and pedagogy, Lionel Tertis is known as one of the first and most influential career violists. Established in 1980, the Lionel Tertis International Viola Competition and Festival was founded in his honor and occurs triennially at the Isle of Man.

Highly active in the fields of viola performance, composition, recording, and pedagogy, Lionel Tertis is known as one of the first and most influential career violists. Established in 1980, the Lionel Tertis International Viola Competition and Festival was founded in his honor and occurs triennially at the Isle of Man. While addressing facets of the professional violist with workshops, lectures, and masterclasses, this event provides a venue for competitive performers, acting as a platform for new viola repertoire.

Each competitor must prepare an extensive set of viola repertoire, among which is a compulsory piece for unaccompanied viola by an English composer. These commissioned works require the virtuosity and expression available within a contemporary musical language; this additionally challenges competitors to provide an artistic interpretation relatively untouched by tradition or common practice.

Although these pieces are written specifically for the competition, the commissioned works have the capacity to reach beyond the competition sphere and are highly programmable in most recital and solo performance settings. These pieces provide the contemporary violist with a greater selection of repertoire that displays idiomatic and expressive strengths of the viola.

My project commemorates the contributions of Lionel Tertis to the advancement of viola repertoire and performance with the study of works written a century post his prolific career. The secondary intent is to provide biographical information about each composer and to explore how these highly programmable works enrich the violist and their repertoire, ultimately bringing recognition to these new works for solo viola. Through biographical research, musical analysis, interviews and the recording process, I will provide a performer's analysis and supplemental recordings for three of these works: Darkness Draws In by David Matthews, Sonatine I by Roger Steptoe and Through a Limbeck by John Woolrich.
ContributorsWuenschel, Allyson Kay (Author) / Buck, Nancy (Thesis advisor) / Carpenter, Ellon (Committee member) / Ryan, Russell (Committee member) / Arizona State University (Publisher)
Created2017
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This handbook is aimed to develop a violist’s technique as they move from Georg Philipp Telemann’s Concerto for Viola, Strings, and Basso Continuo in G Major, TWV 51: G9 and begin the Carl Stamitz's Viola Concerto in D Major, Op. 1. Ten etudes and related exercises introduce and highlight various

This handbook is aimed to develop a violist’s technique as they move from Georg Philipp Telemann’s Concerto for Viola, Strings, and Basso Continuo in G Major, TWV 51: G9 and begin the Carl Stamitz's Viola Concerto in D Major, Op. 1. Ten etudes and related exercises introduce and highlight various techniques, providing a comprehensive and methodical transition from one concerto to the next. These etudes are based on fragments of the Stamitz Concerto in an effort to directly relate technical development with performance skills.
ContributorsChien, Shao-Chuan Sylvia (Author) / Buck, Nancy (Thesis advisor) / Rockmaker, Jody (Committee member) / Landschoot, Thomas (Committee member) / Arizona State University (Publisher)
Created2018