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- All Subjects: Environmental engineering
- Creators: Fox, Peter
- Creators: Rittmann, Bruce E.
- Member of: ASU Electronic Theses and Dissertations
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 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
Description
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
Description
ABSTRACT External accountability is embedded in every school system across the United States. This dissertation study focuses on how ten principals negotiate the accountability system placed upon their school by the state of Arizona. The federal accountability policy, No Child Left Behind (NCLB), requires that states use a standardized assessment to document student achievement. Arizona's policy to meet the federal requirements of NCLB is Arizona Learns (AZLearns). AZLearns outlines the formulas for determining which schools are achieving and which schools need to improve. Each school is tagged with a label annually. The labels are Excelling, Highly Performing, Performing Plus, Performing, Underperforming and Failing. The foundation of this study lies in the interpretation, application and negotiation of a school's label by its principal. To investigate the relationship between external accountability and the daily life of a principal, I interviewed ten Arizona elementary school principals. The research questions of this study are: (R1) What effects do external accountability measures have on the development of the organizational capacity of a school? (R2) How do Arizona principals negotiate their school's assigned label in their everyday professional practice? (R3) What are Arizona principals' views of the state accountability process? A qualitative, phenomenological research methodology was used to interview the participants and analyze their stories for common themes. The commonalities that surfaced across the experiences of the principals in response to the labels placed on their school are Accountability, Achievement and Attitude. This study found that Accountability was based on multiple interpretations of policies enforced by the federal government, state or district guidelines and parent or school expectations. Achievement was a result of multiple factors including data collected from test scores, the quality of teachers or instruction and the personal goals of the principals. Attitude was a process embedded in the high stakes testing era, boundaries or conflicts within the location of the school and the personal experiences of the principals. This research is an attempt to share the multiple voices of principals that may lead to alternative meanings or even provoke questions about the labeling system in Arizona schools.
ContributorsMcNeil, David Michael (Author) / Davey, Lynn (Thesis advisor) / Mccarty, Teresa (Committee member) / Donofrio, Robert (Committee member) / Arizona State University (Publisher)
Created2011
Description
There is a nationwide gap in which African American, Hispanic and low-income students perform significantly lower than their peers. Research suggests that teachers hold lower expectations for these students resulting in lower achievement. There are four main factors that influence teacher expectations: stereotypes, teacher self-efficacy, school culture, language and formal policies and programs aimed at increasing teacher expectations. The purpose of this study was to inquire into the following questions: (1) What are the factors that influence teachers' academic expectations for low-income and minority students? (2) What are teacher's perceptions on the effectiveness of formal policies and programs that are aimed at increasing teacher expectations? More specifically, do teachers feel that top-down formal policies, such as teacher evaluations, uniform curriculum, and performance-based pay are effective in impacting their expectations, or do teachers believe that bottom-up policies, such as book studies and professional learning communities, make more of an impact on increasing their expectations? Ten teachers were interviewed in a school district that is consistent with the state and national achievement gap. The findings revealed that teacher expectations are influenced by the four factors I found in the research as well as two other factors: a cultural disconnect among teachers and students and teachers' level of motivation. A combination of top-down and bottom-up formal policies and programs are needed as teachers are individuals and all respond to various forms of formal policies and programs differently.
ContributorsCraig, Tina (Author) / Mccarty, Teresa (Thesis advisor) / Davey, Lynn (Committee member) / Miller, Lynn (Committee member) / Arizona State University (Publisher)
Created2011
Description
Local municipalities in the Phoenix Metropolitan Area have voiced an interest in purchasing alternate source water with lower DBP precursors. Along the primary source is a hydroelectric dam in which water will be diverted from. This project is an assessment of optimizing the potential blends of source water to a water treatment plant in an effort to enable them to more readily meet DBP regulations. To perform this analysis existing water treatment models were used in conjunction with historic water quality sampling data to predict chemical usage necessary to meet DBP regulations. A retrospective analysis was performed for the summer months of 2007 regarding potential for the WTP to reduce cost through optimizing the source water by an average of 30% over the four-month period, accumulating to overall treatment savings of $154 per MG ($82 per AF).
ContributorsRice, Jacelyn (Author) / Westerhoff, Paul (Thesis advisor) / Fox, Peter (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2011
Analysis of photocatalysis for precursor removal and formation inhibition of disinfection byproducts
Description
Disinfection byproducts are the result of reactions between natural organic matter (NOM) and a disinfectant. The formation and speciation of DBP formation is largely dependent on the disinfectant used and the natural organic matter (NOM) concentration and composition. This study examined the use of photocatalysis with titanium dioxide for the oxidation and removal of DBP precursors (NOM) and the inhibition of DBP formation. Water sources were collected from various points in the treatment process, treated with photocatalysis, and chlorinated to analyze the implications on total trihalomethane (TTHM) and the five haloacetic acids (HAA5) formations. The three sub-objectives for this study included: the comparison of enhanced and standard coagulation to photocatalysis for the removal of DBP precursors; the analysis of photocatalysis and characterization of organic matter using size exclusion chromatography and fluorescence spectroscopy and excitation-emission matrices; and the analysis of photocatalysis before GAC filtration. There were consistencies in the trends for each objective including reduced DBP precursors, measured as dissolved organic carbon DOC concentration and UV absorbance at 254 nm. Both of these parameters decreased with increased photocatalytic treatment and could be due in part to the adsorption to as well as the oxidation of NOM on the TiO2 surface. This resulted in lower THM and HAA concentrations at Medium and High photocatalytic treatment levels. However, at No UV exposure and Low photocatalytic treatment levels where oxidation reactions were inherently incomplete, there was an increase in THM and HAA formation potential, in most cases being significantly greater than those found in the raw water or Control samples. The size exclusion chromatography (SEC) results suggest that photocatalysis preferentially degrades the higher molecular mass fraction of NOM releasing lower molecular mass (LMM) compounds that have not been completely oxidized. The molecular weight distributions could explain the THM and HAA formation potentials that decreased at the No UV exposure samples but increased at Low photocatalytic treatment levels. The use of photocatalysis before GAC adsorption appears to increase bed life of the contactors; however, higher photocatalytic treatment levels have been shown to completely mineralize NOM and would therefore not require additional GAC adsorption after photocatalysis.
ContributorsDaugherty, Erin (Author) / Abbaszadegan, Morteza (Thesis advisor) / Fox, Peter (Committee member) / Mayer, Brooke (Committee member) / Arizona State University (Publisher)
Created2011
Description
To address sustainability issues in wastewater treatment (WWT), Siemens Water Technologies (SWT) has designed a "hybrid" process that couples common activated sludge (AS) and anaerobic digestion (AD) technologies with the novel concepts of AD sludge recycle and biosorption. At least 85% of the hybrid's AD sludge is recycled to the AS process, providing additional sorbent for influent particulate chemical oxygen demand (PCOD) biosorption in contact tanks. Biosorbed PCOD is transported to the AD, where it is converted to methane. The aim of this study is to provide mass balance and microbial community analysis (MCA) of SWT's two hybrid and one conventional pilot plant trains and mathematical modeling of the hybrid process including a novel model of biosorption. A detailed mass balance was performed on each tank and the overall system. The mass balance data supports the hybrid process is more sustainable: It produces 1.5 to 5.5x more methane and 50 to 83% less sludge than the conventional train. The hybrid's superior performance is driven by 4 to 8 times longer solid retention times (SRTs) as compared to conventional trains. However, the conversion of influent COD to methane was low at 15 to 22%, and neither train exhibited significant nitrification or denitrification. Data were inconclusive as to the role of biosorption in the processes. MCA indicated the presence of Archaea and nitrifiers throughout both systems. However, it is inconclusive as to how active Archaea and nitrifiers are under anoxic, aerobic, and anaerobic conditions. Mathematical modeling confirms the hybrid process produces 4 to 20 times more methane and 20 to 83% less sludge than the conventional train under various operating conditions. Neither process removes more than 25% of the influent nitrogen or converts more that 13% to nitrogen gas due to biomass washout in the contact tank and short SRTs in the stabilization tank. In addition, a mathematical relationship was developed to describe PCOD biosorption through adsorption to biomass and floc entrapment. Ultimately, process performance is more heavily influenced by the higher AD SRTs attained when sludge is recycled through the system and less influenced by the inclusion of biosorption kinetics.
ContributorsYoung, Michelle Nichole (Author) / Rittmann, Bruce E. (Thesis advisor) / Fox, Peter (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2011
Description
Lipids and free fatty acids (FFA) from cyanobacterium Synechocystis can be used for biofuel (e.g. biodiesel or renewable diesel) production. In order to utilize and scale up this technique, downstream processes including culturing and harvest, cell disruption, and extraction were studied. Several solvents/solvent systems were screened for lipid extraction from Synechocystis. Chloroform + methanol-based Folch and Bligh & Dyer methods were proved to be "gold standard" for small-scale analysis due to their highest lipid recoveries that were confirmed by their penetration of the cell membranes, higher polarity, and stronger interaction with hydrogen bonds. Less toxic solvents, such as methanol and MTBE, or direct transesterification of biomass (without pre-extraction step) gave only slightly lower lipid-extraction yields and can be considered for large-scale application. Sustained exposure to high and low temperature extremes severely lowered the biomass and lipid productivity. Temperature stress also triggered changes of lipid quality such as the degree of unsaturation; thus, it affected the productivities and quality of Synechocystis-derived biofuel. Pulsed electric field (PEF) was evaluated for cell disruption prior to lipid extraction. A treatment intensity > 35 kWh/m3 caused significant damage to the plasma membrane, cell wall, and thylakoid membrane, and it even led to complete disruption of some cells into fragments. Treatment by PEF enhanced the potential for the low-toxicity solvent isopropanol to access lipid molecules during subsequent solvent extraction, leading to lower usage of isopropanol for the same extraction efficiency. Other cell-disruption methods also were tested. Distinct disruption effects to the cell envelope, plasma membrane, and thylakoid membranes were observed that were related to extraction efficiency. Microwave and ultrasound had significant enhancement of lipid extraction. Autoclaving, ultrasound, and French press caused significant release of lipid into the medium, which may increase solvent usage and make medium recycling difficult. Production of excreted FFA by mutant Synechocystis has the potential of reducing the complexity of downstream processing. Major problems, such as FFA precipitation and biodegradation by scavengers, account for FFA loss in operation. Even a low concentration of FFA scavengers could consume FFA at a high rate that outpaced FFA production rate. Potential strategies to overcome FFA loss include high pH, adsorptive resin, and sterilization techniques.
ContributorsSheng, Chieh (Author) / Rittmann, Bruce E. (Thesis advisor) / Westerhoff, Paul (Committee member) / Vermaas, Willem (Committee member) / Arizona State University (Publisher)
Created2011
Description
As schools across Arizona worked to meet NCLB's AYP requirement in 2010-2011, they were also labeled and sanctioned by AZ Learns. This phenomenological study focused on six effective high school principals in two Arizona school districts to ascertain how accountability policies impacted the principals' job responsibilities, autonomy, and ability to pursue social justice on their campuses. Interviews were conducted in three phases: superintendents, three principals from the superintendents' recommendations of effective school leaders, and three teachers from each school. In addition to analysis of individual principal leadership patterns, comparisons were made across districts, and from school to school within the same district. The goal of the study was to determine if and how principals were able to accomplish their goals for their school. The principals' leadership styles were examined through a Vortex Leadership Framework that posited principals at the center of a vortex of varying leadership roles, interests, and external forces, including accountability, autonomy, and limited resources. Key findings included (a) high school principals' responsibilities now include selling change to their staff, (b) principals' accountability is limited more by district constraints than by state or federal accountability, (c) principals must contend with rigid one-size fits all accountability standards that do not always meet the needs of their students, and (d) principals' autonomy is tied to their resources, including funding for staffing and programs.
ContributorsBatsell, Holly (Author) / Powers, Jeanne M. (Thesis advisor) / Mccarty, Teresa (Committee member) / Davey, Lynn (Committee member) / Arizona State University (Publisher)
Created2013
Description
Many manmade chemicals used in consumer products are ultimately washed down the drain and are collected in municipal sewers. Efficient chemical monitoring at wastewater treatment (WWT) plants thus may provide up-to-date information on chemical usage rates for epidemiological assessments. The objective of the present study was to extrapolate this concept, termed 'sewage epidemiology', to include municipal sewage sludge (MSS) in identifying and prioritizing contaminants of emerging concern (CECs). To test this the following specific aims were defined: i) to screen and identify CECs in nationally representative samples of MSS and to provide nationwide inventories of CECs in U.S. MSS; ii) to investigate the fate and persistence in MSS-amended soils, of sludge-borne hydrophobic CECs; and iii) to develop an analytical tool relying on contaminant levels in MSS as an indicator for identifying and prioritizing hydrophobic CECs. Chemicals that are primarily discharged to the sewage systems (alkylphenol surfactants) and widespread persistent organohalogen pollutants (perfluorochemicals and brominated flame retardants) were analyzed in nationally representative MSS samples. A meta-analysis showed that CECs contribute about 0.04-0.15% to the total dry mass of MSS, a mass equivalent of 2,700-7,900 metric tonnes of chemicals annually. An analysis of archived mesocoms from a sludge weathering study showed that 64 CECs persisted in MSS/soil mixtures over the course of the experiment, with half-lives ranging between 224 and >990 days; these results suggest an inherent persistence of CECs that accumulate in MSS. A comparison of the spectrum of chemicals (n=52) analyzed in nationally representative biological specimens from humans and MSS revealed 70% overlap. This observed co-occurrence of contaminants in both matrices suggests that MSS may serve as an indicator for ongoing human exposures and body burdens of pollutants in humans. In conclusion, I posit that this novel approach in sewage epidemiology may serve to pre-screen and prioritize the several thousands of known or suspected CECs to identify those that are most prone to pose a risk to human health and the environment.
ContributorsVenkatesan, Arjunkrishna (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2013