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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
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Description
This dissertation focused on the development and application of state-of-the-art monitoring tools and analysis methods for tracking the fate of trace level contaminants in the natural and built water environments, using fipronil as a model; fipronil and its primary degradates (known collectively as fiproles) are among a group of trace

This dissertation focused on the development and application of state-of-the-art monitoring tools and analysis methods for tracking the fate of trace level contaminants in the natural and built water environments, using fipronil as a model; fipronil and its primary degradates (known collectively as fiproles) are among a group of trace level emerging environmental contaminants that are extremely potent arthropodic neurotoxins. The work further aimed to fill in data gaps regarding the presence and fate of fipronil in engineered water systems, specifically in a wastewater treatment plant (WWTP), and in an engineered wetland. A review of manual and automated “active” water sampling technologies motivated the development of two new automated samplers capable of in situ biphasic extraction of water samples across the bulk water/sediment interface of surface water systems. Combined with an optimized method for the quantification of fiproles, the newly developed In Situ Sampler for Biphasic water monitoring (IS2B) was deployed along with conventional automated water samplers, to study the fate and occurrence of fiproles in engineered water environments; continuous sampling over two days and subsequent analysis yielded average total fiprole concentrations in wetland surface water (9.9 ± 4.6 to 18.1 ± 4.6 ng/L) and wetland sediment pore water (9.1 ± 3.0 to 12.6 ± 2.1 ng/L). A mass balance of the WWTP located immediately upstream demonstrated unattenuated breakthrough of total fiproles through the WWTP with 25 ± 3 % of fipronil conversion to degradates, and only limited removal of total fiproles in the wetland (47 ± 13%). Extrapolation of local emissions (5–7 g/d) suggests nationwide annual fiprole loadings from WWTPs to U.S. surface waters on the order of about one half to three quarters of a metric tonne. The qualitative and quantitative data collected in this work have regulatory implications, and the sampling tools and analysis strategies described in this thesis have broad applicability in the assessment of risks posed by trace level environmental contaminants.
ContributorsSupowit, Samuel (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Johnson, Paul C (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Potential-Induced Degradation (PID) is an extremely serious photovoltaic (PV) durability issue significantly observed in crystalline silicon PV modules due to its rapid power degradation, particularly when compared to other PV degradation modes. The focus of this dissertation is to understand PID mechanisms and to develop PID-free cells and modules. PID-affected

Potential-Induced Degradation (PID) is an extremely serious photovoltaic (PV) durability issue significantly observed in crystalline silicon PV modules due to its rapid power degradation, particularly when compared to other PV degradation modes. The focus of this dissertation is to understand PID mechanisms and to develop PID-free cells and modules. PID-affected modules have been claimed to be fully recovered by high temperature and reverse potential treatments. However, the results obtained in this work indicate that the near-full recovery of efficiency can be achieved only at high irradiance conditions, but the full recovery of efficiency at low irradiance levels, of shunt resistance, and of quantum efficiency (QE) at short wavelengths could not be achieved. The QE loss observed at short wavelengths was modeled by changing the front surface recombination velocity. The QE scaling error due to a measurement on a PID shunted cell was addressed by developing a very low input impedance accessory applicable to an existing QE system. The impacts of silicon nitride (SiNx) anti-reflection coating (ARC) refractive index (RI) and emitter sheet resistance on PID are presented. Low RI ARC cells (1.87) were observed to be PID-susceptible whereas high RI ARC cells (2.05) were determined to be PID-resistant using a method employing high dose corona charging followed by time-resolved measurement of surface voltage. It has been demonstrated that the PID could be prevented by deploying an emitter having a low sheet resistance (~ 60 /sq) even if a PID-susceptible ARC is used in a cell. Secondary ion mass spectroscopy (SIMS) results suggest that a high phosphorous emitter layer hinders sodium transport, which is responsible for the PID. Cells can be screened for PID susceptibility by illuminated lock-in thermography (ILIT) during the cell fabrication process, and the sample structure for this can advantageously be simplified as long as the sample has the SiNx ARC and an aluminum back surface field. Finally, this dissertation presents a prospective method for eliminating or minimizing the PID issue either in the factory during manufacturing or in the field after system installation. The method uses commercially available, thin, and flexible Corning® Willow® Glass sheets or strips on the PV module glass superstrates, disrupting the current leakage path from the cells to the grounded frame.
ContributorsOh, Jaewon (Author) / Bowden, Stuart (Thesis advisor) / Tamizhmani, Govindasamy (Thesis advisor) / Honsberg, Christiana (Committee member) / Hacke, Peter (Committee member) / Schroder, Dieter (Committee member) / Arizona State University (Publisher)
Created2016
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Description
N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air

N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air and water. The goal of this dissertation was to contribute to closing these knowledge gaps on potential human NDMA exposure through contributions to atmospheric measurements and fate as well as aqueous formation processes.

Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.

NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.

NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
ContributorsZhang, Jinwei (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The popularity of solar photovoltaic (PV) energy is growing across the globe with more than 500 GW installed in 2018 with a capacity of 640 GW in 2019. Improved PV module reliability minimizes the levelized cost of energy. Studying and accelerating encapsulant browning and solder bond degradation—two of the most

The popularity of solar photovoltaic (PV) energy is growing across the globe with more than 500 GW installed in 2018 with a capacity of 640 GW in 2019. Improved PV module reliability minimizes the levelized cost of energy. Studying and accelerating encapsulant browning and solder bond degradation—two of the most commonly observed degradation modes in the field—in a lab requires replicating the stress conditions that induce the same field degradation modes in a controlled accelerated environment to reduce testing time.

Accelerated testing is vital in learning about the reliability of solar PV modules. The unique streamlined approach taken saves time and resources with a statistically significant number of samples being tested in one chamber under multiple experimental stress conditions that closely mirror field conditions that induce encapsulant browning and solder bond degradation. With short circuit current (Isc) and series resistance (Rs) degradation data sets at multiple temperatures, the activation energies (Ea) for encapsulant browning and solder bond degradation was calculated.

Regular degradation was replaced by the wear-out stages of encapsulant browning and solder bond degradation by subjecting two types of field-aged modules to further accelerated testing. For browning, the Ea calculated through the Arrhenius model was 0.37 ± 0.17 eV and 0.71 ± 0.07 eV. For solder bond degradation, the Arrhenius model was used to calculate an Ea of 0.12 ± 0.05 eV for solder with 2wt% Ag and 0.35 ± 0.04 eV for Sn60Pb40 solder.

To study the effect of types of encapsulant, backsheet, and solder on encapsulant browning and solder bond degradation, 9-cut-cell samples maximizing available data points while minimizing resources underwent accelerated tests described for modules. A ring-like browning feature was observed in samples with UV pass EVA above and UV cut EVA below the cells. The backsheet permeability influences the extent of oxygen photo-bleaching. In samples with solder bond degradation, increased bright spots and cell darkening resulted in increased Rs. Combining image processing with fluorescence imaging and electroluminescence imaging would yield great insight into the two degradation modes.
ContributorsGopalakrishna, Hamsini (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Rogers, Bradley (Committee member) / Hacke, Peter (Committee member) / Arizona State University (Publisher)
Created2020
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Description
An ongoing effort in the photovoltaic (PV) industry is to reduce the major manufacturing cost components of solar cells, the great majority of which are based on crystalline silicon (c-Si). This includes the substitution of screenprinted silver (Ag) cell contacts with alternative copper (Cu)-based contacts, usually applied with plating. Plated

An ongoing effort in the photovoltaic (PV) industry is to reduce the major manufacturing cost components of solar cells, the great majority of which are based on crystalline silicon (c-Si). This includes the substitution of screenprinted silver (Ag) cell contacts with alternative copper (Cu)-based contacts, usually applied with plating. Plated Cu contact schemes have been under study for many years with only minor traction in industrial production. One of the more commonly-cited barriers to the adoption of Cu-based contacts for photovoltaics is long-term reliability, as Cu is a significant contaminant in c-Si, forming precipitates that degrade performance via degradation of diode character and reduction of minority carrier lifetime. Cu contamination from contacts might cause degradation during field deployment if Cu is able to ingress into c-Si. Furthermore, Cu contamination is also known to cause a form of light-induced degradation (LID) which further degrades carrier lifetime when cells are exposed to light.

Prior literature on Cu-contact reliability tended to focus on accelerated testing at the cell and wafer level that may not be entirely replicative of real-world environmental stresses in PV modules. This thesis is aimed at advancing the understanding of Cu-contact reliability from the perspective of quasi-commercial modules under more realistic stresses. In this thesis, c-Si solar cells with Cu-plated contacts are fabricated, made into PV modules, and subjected to environmental stress in an attempt to induce hypothesized failure modes and understand any new vulnerabilities that Cu contacts might introduce. In particular, damp heat stress is applied to conventional, p-type c-Si modules and high efficiency, n-type c-Si heterojunction modules. I present evidence of Cu-induced diode degradation that also depends on PV module materials, as well as degradation unrelated to Cu, and in either case suggest engineering solutions to the observed degradation. In a forensic search for degradation mechanisms, I present novel evidence of Cu outdiffusion from contact layers and encapsulant-driven contact corrosion as potential key factors. Finally, outdoor exposures to light uncover peculiarities in Cu-plated samples, but do not point to especially serious vulnerabilities.
ContributorsKaras, Joseph (Author) / Bowden, Stuart (Thesis advisor) / Alford, Terry (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Michaelson, Lynne (Committee member) / Arizona State University (Publisher)
Created2020