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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
ABSTRACT As the use of photovoltaic (PV) modules in large power plants continues to increase globally, more studies on degradation, reliability, failure modes, and mechanisms of field aged modules are needed to predict module life expectancy based on accelerated lifetime testing of PV modules. In this work, a 26+ year

ABSTRACT As the use of photovoltaic (PV) modules in large power plants continues to increase globally, more studies on degradation, reliability, failure modes, and mechanisms of field aged modules are needed to predict module life expectancy based on accelerated lifetime testing of PV modules. In this work, a 26+ year old PV power plant in Phoenix, Arizona has been evaluated for performance, reliability, and durability. The PV power plant, called Solar One, is owned and operated by John F. Long's homeowners association. It is a 200 kWdc, standard test conditions (STC) rated power plant comprised of 4000 PV modules or frameless laminates, in 100 panel groups (rated at 175 kWac). The power plant is made of two center-tapped bipolar arrays, the north array and the south array. Due to a limited time frame to execute this large project, this work was performed by two masters students (Jonathan Belmont and Kolapo Olakonu) and the test results are presented in two masters theses. This thesis presents the results obtained on the south array and the other thesis presents the results obtained on the north array. Each of these two arrays is made of four sub arrays, the east sub arrays (positive and negative polarities) and the west sub arrays (positive and negative polarities), making up eight sub arrays. The evaluation and analyses of the power plant included in this thesis consists of: visual inspection, electrical performance measurements, and infrared thermography. A possible presence of potential induced degradation (PID) due to potential difference between ground and strings was also investigated. Some installation practices were also studied and found to contribute to the power loss observed in this investigation. The power output measured in 2011 for all eight sub arrays at STC is approximately 76 kWdc and represents a power loss of 62% (from 200 kW to 76 kW) over 26+ years. The 2011 measured power output for the four south sub arrays at STC is 39 kWdc and represents a power loss of 61% (from 100 kW to 39 kW) over 26+ years. Encapsulation browning and non-cell interconnect ribbon breakages were determined to be the primary causes for the power loss.
ContributorsOlakonu, Kolapo (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Rogers, Bradley (Committee member) / Arizona State University (Publisher)
Created2012
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Description
This is a two-part thesis: Part 1 of this thesis tests and validates the methodology and mathematical models of the International Electrotechnical Commission (IEC) 61853-2 standard for the measurement of angle of incidence (AOI) effects on photovoltaic modules. Flat-plate photovoltaic modules in the field operate under a wide range of

This is a two-part thesis: Part 1 of this thesis tests and validates the methodology and mathematical models of the International Electrotechnical Commission (IEC) 61853-2 standard for the measurement of angle of incidence (AOI) effects on photovoltaic modules. Flat-plate photovoltaic modules in the field operate under a wide range of environmental conditions. The purpose of IEC 61853-2 is to characterize photovoltaic modules' performance under specific environmental conditions. Part 1 of this report focuses specifically on AOI. To accurately test and validate IEC 61853-2 standard for measuring AOI, meticulous experimental setup and test procedures were followed. Modules of five different photovoltaic technology types with glass superstrates were tested. Test results show practically identical relative light transmission plots for all five test modules. The experimental results were compared to theoretical and empirical models for relative light transmission of air-glass interface. IEC 61853-2 states "for the flat glass superstrate modules, the AOI test does not need to be performed; rather, the data of a flat glass air interface can be used." The results obtained in this thesis validate this statement. This work was performed in collaboration with another Master of Science student (Surynarayana Janakeeraman) and the test results are presented in two masters theses. Part 2 of this thesis is to develop non-intrusive techniques to accurately measure the quantum efficiency (QE) of a single-junction crystalline silicon cell within a commercial module. This thesis will describe in detail all the equipment and conditions necessary to measure QE and discuss the factors which may influence this measurement. The ability to utilize a non-intrusive test to measure quantum efficiency of a cell within a module is extremely beneficial for reliability testing of commercial modules. Detailed methodologies for this innovative test procedure are not widely available in industry because equipment and measurement techniques have not been explored extensively. This paper will provide a literature review describing relevant theories and measurement techniques related to measuring the QE of a cell within a module. The testing methodology and necessary equipment will be described in detail. Results and conclusions provide the overall accuracy of the measurements and discuss the parameters affecting these measurements.
ContributorsKnisely, Brett (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Rogers, Bradley (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Photovoltaic (PV) systems are one of the next generation's renewable energy sources for our world energy demand. PV modules are highly reliable. However, in polluted environments, over time, they will collect grime and dust. There are also limited field data studies about soiling losses on PV modules. The study showed

Photovoltaic (PV) systems are one of the next generation's renewable energy sources for our world energy demand. PV modules are highly reliable. However, in polluted environments, over time, they will collect grime and dust. There are also limited field data studies about soiling losses on PV modules. The study showed how important it is to investigate the effect of tilt angle on soiling. The study includes two sets of mini-modules. Each set has 9 PV modules tilted at 0, 5, 10, 15, 20, 23, 30, 33 and 40°. The first set called "Cleaned" was cleaned every other day. The second set called "Soiled" was never cleaned after the first day. The short circuit current, a measure of irradiance, and module temperature was monitored and recorded every two minutes over three months (January-March 2011). The data were analyzed to investigate the effect of tilt angle on daily and monthly soiling, and hence transmitted solar insolation and energy production by PV modules. The study shows that during the period of January through March 2011 there was an average loss due to soiling of approximately 2.02% for 0° tilt angle. Modules at tilt anlges 23° and 33° also have some insolation losses but do not come close to the module at 0° tilt angle. Tilt anlge 23° has approximately 1.05% monthly insolation loss, and 33° tilt angle has an insolation loss of approximately 0.96%. The soiling effect is present at any tilt angle, but the magnitude is evident: the flatter the solar module is placed the more energy it will lose.
ContributorsCano Valero, José (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Madakannan, Arunachalanadar (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2011
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Photovoltaic (PV) modules undergo performance degradation depending on climatic conditions, applications, and system configurations. The performance degradation prediction of PV modules is primarily based on Accelerated Life Testing (ALT) procedures. In order to further strengthen the ALT process, additional investigation of the power degradation of field aged PV modules in

Photovoltaic (PV) modules undergo performance degradation depending on climatic conditions, applications, and system configurations. The performance degradation prediction of PV modules is primarily based on Accelerated Life Testing (ALT) procedures. In order to further strengthen the ALT process, additional investigation of the power degradation of field aged PV modules in various configurations is required. A detailed investigation of 1,900 field aged (12-18 years) PV modules deployed in a power plant application was conducted for this study. Analysis was based on the current-voltage (I-V) measurement of all the 1,900 modules individually. I-V curve data of individual modules formed the basis for calculating the performance degradation of the modules. The percentage performance degradation and rates of degradation were compared to an earlier study done at the same plant. The current research was primarily focused on identifying the extent of potential induced degradation (PID) of individual modules with reference to the negative ground potential. To investigate this, the arrangement and connection of the individual modules/strings was examined in detail. The study also examined the extent of underperformance of every series string due to performance mismatch of individual modules in that string. The power loss due to individual module degradation and module mismatch at string level was then compared to the rated value.
ContributorsJaspreet Singh (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Rogers, Bradley (Committee member) / Arizona State University (Publisher)
Created2011
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Description
As engineered nanomaterials (NMs) become used in industry and commerce their loading to sewage will increase. However, the fate of widely used NMs in wastewater treatment plants (WWTPs) remains poorly understood. In this research, sequencing batch reactors (SBRs) were operated with hydraulic (HRT) and sludge (SRT) retention times representative of

As engineered nanomaterials (NMs) become used in industry and commerce their loading to sewage will increase. However, the fate of widely used NMs in wastewater treatment plants (WWTPs) remains poorly understood. In this research, sequencing batch reactors (SBRs) were operated with hydraulic (HRT) and sludge (SRT) retention times representative of full-scale biological WWTPs for several weeks. NM loadings at the higher range of expected environmental concentrations were selected. To achieve the pseudo-equilibrium state concentration of NMs in biomass, SBR experiments needed to operate for more than three times the SRT value, approximately 18 days. Under the conditions tested, NMs had negligible effects on ability of the wastewater bacteria to biodegrade organic material, as measured by chemical oxygen demand (COD). NM mass balance closure was achieved by measuring NMs in liquid effluent and waste biosolids. All NMs were well removed at the typical biomass concentration (1~2 gSS/L). However, carboxy-terminated polymer coated silver nanoparticles (fn-Ag) were removed less effectively (88% removal) than hydroxylated fullerenes (fullerols; >90% removal), nano TiO2 (>95% removal) or aqueous fullerenes (nC60; >95% removal). Although most NMs did not settle out of the feed solution without bacteria present, approximately 65% of the titanium dioxide was removed even in the absence of biomass simply due to self-aggregation and settling. Experiments conducted over 4 months with daily loadings of nC60 showed that nC60 removal from solution depends on the biomass concentration. Under conditions representative of most suspended growth biological WWTPs (e.g., activated sludge), most of the NMs will accumulate in biosolids rather than in liquid effluent discharged to surface waters. Significant fractions of fn-Ag were associated with colloidal material which suggests that efficient particle separation processes (sedimentation or filtration) could further improve removal of NM from effluent. As most NMs appear to accumulate in biosolids, future research should examine the fate of NMs during disposal of WWTP biosolids, which may occur through composting or anaerobic digestion and/or land application, incineration, or landfill disposal.
ContributorsWang, Yifei (Author) / Westerhoff, Paul (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Rittmann, Bruce (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Nanotechnology is becoming increasingly present in our environment. Engineered nanoparticles (ENPs), defined as objects that measure less than 100 nanometers in at least one dimension, are being integrated into commercial products because of their small size, increased surface area, and quantum effects. These special properties have made ENPs antimicrobial agents

Nanotechnology is becoming increasingly present in our environment. Engineered nanoparticles (ENPs), defined as objects that measure less than 100 nanometers in at least one dimension, are being integrated into commercial products because of their small size, increased surface area, and quantum effects. These special properties have made ENPs antimicrobial agents in clothing and plastics, among other applications in industries such as pharmaceuticals, renewable energy, and prosthetics. This thesis incorporates investigations into both application of nanoparticles into polymers as well as implications of nanoparticle release into the environment. First, the integration of ENPs into polymer fibers via electrospinning was explored. Electrospinning uses an external electric field applied to a polymer solution to produce continuous fibers with large surface area and small volume, a quality which makes the fibers ideal for water and air purification purposes. Indium oxide and titanium dioxide nanoparticles were embedded in polyvinylpyrrolidone and polystyrene. Viscosity, critical voltage, and diameter of electrospun fibers were analyzed in order to determine the effects of nanoparticle integration into the polymers. Critical voltage and viscosity of solution increased at 5 wt% ENP concentration. Fiber morphology was not found to change significantly as a direct effect of ENP addition, but as an effect of increased viscosity and surface tension. These results indicate the possibility for seamless integration of ENPs into electrospun polymers. Implications of ENP release were investigated using phase distribution functional assays of nanoscale silver and silver sulfide, as well as photolysis experiments of nanoscale titanium dioxide to quantify hydroxyl radical production. Functional assays are a means of screening the relevant importance of multiple processes in the environmental fate and transport of ENPs. Four functional assays – water-soil, water-octanol, water-wastewater sludge and water-surfactant – were used to compare concentrations of silver sulfide ENPs (Ag2S-NP) and silver ENPs (AgNP) capped by four different coatings. The functional assays resulted in reproducible experiments which clearly showed variations between nanoparticle phase distributions; the findings may be a product of the effects of the different coatings of the ENPs used. In addition to phase distribution experiments, the production of hydroxyl radical (HO•) by nanoscale titanium dioxide (TiO2) under simulated solar irradiation was investigated. Hydroxyl radical are a short-lived, highly reactive species produced by solar radiation in aquatic environments that affect ecosystem function and degrades pollutants. HO• is produced by photolysis of TiO2 and nitrate (NO3-); these two species were used in photolysis experiments to compare the relative loads of hydroxyl radical which nanoscale TiO2 may add upon release to natural waters. Para-chlorobenzoic acid (pCBA) was used as a probe. Measured rates of pCBA oxidation in the presence of various concentrations of TiO2 nanoparticles and NO3- were utilized to calculate pseudo first order rate constants. Results indicate that, on a mass concentration basis in water, TiO2 produces hydroxyl radical steady state concentrations at 1.3 times more than the equivalent amount of NO3-; however, TiO2 concentrations are generally less than one order of magnitude lower than concentrations of NO3-. This has implications for natural waterways as the amount of nanoscale TiO2 released from consumer products into natural waterways increases in proportion to its use.
ContributorsHoogesteijn von Reitzenstein, Natalia (Author) / Westerhoff, Paul (Thesis advisor) / Herckes, Pierre (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2015
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Description
With the application of reverse osmosis (RO) membranes in the wastewater treatment and seawater desalination, the limitation of flux and fouling problems of RO have gained more attention from researchers. Because of the tunable structure and physicochemical properties of nanomaterials, it is a suitable material that can be used to

With the application of reverse osmosis (RO) membranes in the wastewater treatment and seawater desalination, the limitation of flux and fouling problems of RO have gained more attention from researchers. Because of the tunable structure and physicochemical properties of nanomaterials, it is a suitable material that can be used to incorporate with RO to change the membrane performances. Silver is biocidal, which has been used in a variety of consumer products. Recent studies showed that fabricating silver nanoparticles (AgNPs) on membrane surfaces can mitigate the biofouling problem on the membrane. Studies have shown that Ag released from the membrane in the form of either Ag ions or AgNP will accelerate the antimicrobial activity of the membrane. However, the silver release from the membrane will lower the silver loading on the membrane, which will eventually shorten the antimicrobial activity lifetime of the membrane. Therefore, the silver leaching amount is a crucial parameter that needs to be determined for every type of Ag composite membrane.

This study is attempting to compare four different silver leaching test methods, to study the silver leaching potential of the silver impregnated membranes, conducting the advantages and disadvantages of the leaching methods. An In-situ reduction Ag loaded RO membrane was examined in this study. A custom waterjet test was established to create a high-velocity water flow to test the silver leaching from the nanocomposite membrane in a relative extreme environment. The batch leaching test was examined as the most common leaching test method for the silver composite membrane. The cross-flow filtration and dead-end test were also examined to compare the silver leaching amounts.

The silver coated membrane used in this experiment has an initial silver loading of 2.0± 0.51 ug/cm2. The mass balance was conducted for all of the leaching tests. For the batch test, water jet test, and dead-end filtration, the mass balances are all within 100±25%, which is acceptable in this experiment because of the variance of the initial silver loading on the membranes. A bad silver mass balance was observed at cross-flow filtration. Both of AgNP and Ag ions leached in the solution was examined in this experiment. The concentration of total silver leaching into solutions from the four leaching tests are all below the Secondary Drinking Water Standard for silver which is 100 ppb. The cross-flow test is the most aggressive leaching method, which has more than 80% of silver leached from the membrane after 50 hours of the test. The water jet (54 ± 6.9% of silver remaining) can cause higher silver leaching than batch test (85 ± 1.2% of silver remaining) in one-hour, and it can also cause both AgNP and Ag ions leaching from the membrane, which is closer to the leaching condition in the cross-flow test.
ContributorsHan, Bingru (Author) / Westerhoff, Paul (Thesis advisor) / Perreault, Francois (Committee member) / Sinha, Shahnawaz (Committee member) / Arizona State University (Publisher)
Created2017
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The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV

The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV modules lying in the landfills by 2050, that may not become a not-so-sustainable way of sourcing energy since all PV modules could contain certain amount of toxic substances. Currently in the United States, PV modules are categorized as general waste and can be disposed in landfills. However, potential leaching of toxic chemicals and materials, if any, from broken end-of-life modules may pose health or environmental risks. There is no standard procedure to remove samples from PV modules for chemical toxicity testing in the Toxicity Characteristic Leaching Procedure (TCLP) laboratories as per EPA 1311 standard. The main objective of this thesis is to develop an unbiased sampling approach for the TCLP testing of PV modules. The TCLP testing was concentrated only for the laminate part of the modules, as they are already existing recycling technologies for the frame and junction box components of PV modules. Four different sample removal methods have been applied to the laminates of five different module manufacturers: coring approach, cell-cut approach, strip-cut approach, and hybrid approach. These removed samples were sent to two different TCLP laboratories, and TCLP results were tested for repeatability within a lab and reproducibility between the labs. The pros and cons of each sample removal method have been explored and the influence of sample removal methods on the variability of TCLP results has been discussed. To reduce the variability of TCLP results to an acceptable level, additional improvements in the coring approach, the best of the four tested options, are still needed.
ContributorsLeslie, Joswin (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Kuitche, Joseph (Committee member) / Arizona State University (Publisher)
Created2018
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Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential

Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential health concerns in case of exposure to popular FRs. Carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) have been studied and applied to polymer composites and electronics extensively due to their remarkable properties. Hence CNMs are considered as potential alternative materials that present high flame retardancy. In this research, different kinds of CNMs coatings on polyester fabric are produced and evaluated for their use as flame retardants. To monitor the mass loading of CNMs coated on the fabric, a two-step analytical method for quantifying CNMs embedded in polymer composites was developed. This method consisted of polymer dissolution process using organic solvents followed by subsequent programmed thermal analysis (PTA). This quantification technique was applicable to CNTs with and without high metal impurities in a broad range of polymers. Various types of CNMs were coated on polyester fabric and the efficacy of coatings as flame retardant was evaluated. The oxygen content of CNMs emerged as a critical parameter impacting flame retardancy with higher oxygen content resulting in less FR efficacy. The most performant nanomaterials, multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nantoubes (NH2-MWCNT) showed similar FR properties to current flame retardants with low mass loading (0.18 g/m2) and hence are promising alternatives that warrant further investigation. Chemical/physical modification of MWCNTs was conducted to produce well-dispersed MWCNT solutions without involving oxygen for uniform FR coating. The MWCNTs coating was studied to evaluate the durability of the coating and the impact on the efficacy during use phase by conducting mechanical abrasion and washing test. Approximately 50% and 40% of MWCNTs were released from 1 set of mechanical abrasion and washing test respectively. The losses during simulated usage impacted the flame retardancy negatively.
ContributorsNosaka, Takayuki (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Wang, Qing Hua (Committee member) / Arizona State University (Publisher)
Created2018