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- All Subjects: Civil Engineering
- Creators: Fox, Peter
- Resource Type: Text
Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
Description
This study was devised to elucidate key information concerning the potential risk posed by Legionella in reclaimed water. A series of biological experiments and a recharge basin soil column study were conducted to examine the survival, growth, and transport of L. pneumophila through engineered reclaimed water systems. A pilot-scale, column study was set up to measure Legionella transport in the columns under Arizona recharge basin conditions. Two columns, A and B, were packed to a depth of 122 cm with a loamy sand media collected from a recharge basin in Mesa, Arizona. The grain size distribution of Column A differed from that of Column B by the removal of fines passing the #200 sieve. The different soil profiles represented by column A and B allowed for further investigation of soil attributes which influence the microbial transport mechanism. Both clear PVC columns stand at a height of 1.83 m with an inner diameter of 6.35 cm. Sampling ports were drilled into the column at the soil depths 15, 30, 60, 92, 122 cm. Both columns were acclimated with tertiary treated waste water and set to a flow rate of approximately 1.5 m/d. The columns were used to assess the transport of a bacterial indicator, E. coli, in addition to assessing the study's primary pathogen of concern, Legionella. Approximately, 〖10〗^7 to 〖10〗^9 E. coli cells or 〖10〗^6 to 〖10〗^7Legionella cells were spiked into the columns' head waters for each experiment. Periodically, samples were collected from each column's sampling ports, until a minimum of three pore volume passed through the columns.
The pilot-scale, column study produced novel results which demonstrated the mechanism for Legionella to be transported through recharge basin soil. E. coli was transported, through 122 cm of the media in under 6 hours, whereas, Legionella was transported, through the same distance, in under 30 hours. Legionella has been shown to survive in low nutrient conditions for over a year. Given the novel results of this proof of concept study, a claim can be made for the transport of Legionella into groundwater aquifers through engineering recharge basin conditions, in Central Arizona.
The pilot-scale, column study produced novel results which demonstrated the mechanism for Legionella to be transported through recharge basin soil. E. coli was transported, through 122 cm of the media in under 6 hours, whereas, Legionella was transported, through the same distance, in under 30 hours. Legionella has been shown to survive in low nutrient conditions for over a year. Given the novel results of this proof of concept study, a claim can be made for the transport of Legionella into groundwater aquifers through engineering recharge basin conditions, in Central Arizona.
ContributorsMcBurnett, Lauren Rae (Author) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2014
Description
Flooding is a critical issue around the world, and the absence of comprehension of watershed hydrologic reaction results in lack of lead-time for flood forecasting and expensive harm to property and life. It happens when water flows due to extreme rainfall storm, dam breach or snowmelt exceeds the capacity of river system reservoirs and channels. The objective of this research was to develop a methodology for determining a time series operation for releases through control gates of river-reservoir systems during flooding events in a real-time using one- and/or two-dimensional modeling of flows through river-reservoir systems.
The optimization-simulation methodology interfaces several simulation-software coupled together with an optimization model solved by genetic algorithm coded in MATLAB. These software include the U.S. Army Corps of Engineers HEC-RAS linked the genetic algorithm in MATLAB to come up with an optimization-simulation model for time series gate openings to control downstream elevations. The model involves using the one- and two-dimensional ability in HEC-RAS to perform hydrodynamic routing with high-resolution raster Digital Elevation Models. Also, the model uses both real-time gridded- and gaged-rainfall data in addition to a model for forecasting future rainfall-data.
This new model has been developed to manage reservoir release schedules before, during, and after an extraordinary rainfall event that could cause extreme flooding. Further to observe and control downstream water surface elevations to avoid exceedance of threshold of flood levels in target cells in the downstream area of study, and to minimize the damage and direct effects in both the up and downstream.
The application of the complete optimization-simulation model was applied to a portion of the Cumberland River System in Nashville, Tennessee for the flooding event of May 2010. The objective of this application is to demonstrate the applicability of the model for minimizing flood damages for an actual flood event in real-time on an actual river basin. The purpose of the application in a real-time framework would be to minimize the flood damages at Nashville, Tennessee by keeping the flood stages under the 100-year flood stage. This application also compared the three unsteady flow simulation scenarios: one-dimensional, two-dimensional and combined one- and two-dimensional unsteady flow.
The optimization-simulation methodology interfaces several simulation-software coupled together with an optimization model solved by genetic algorithm coded in MATLAB. These software include the U.S. Army Corps of Engineers HEC-RAS linked the genetic algorithm in MATLAB to come up with an optimization-simulation model for time series gate openings to control downstream elevations. The model involves using the one- and two-dimensional ability in HEC-RAS to perform hydrodynamic routing with high-resolution raster Digital Elevation Models. Also, the model uses both real-time gridded- and gaged-rainfall data in addition to a model for forecasting future rainfall-data.
This new model has been developed to manage reservoir release schedules before, during, and after an extraordinary rainfall event that could cause extreme flooding. Further to observe and control downstream water surface elevations to avoid exceedance of threshold of flood levels in target cells in the downstream area of study, and to minimize the damage and direct effects in both the up and downstream.
The application of the complete optimization-simulation model was applied to a portion of the Cumberland River System in Nashville, Tennessee for the flooding event of May 2010. The objective of this application is to demonstrate the applicability of the model for minimizing flood damages for an actual flood event in real-time on an actual river basin. The purpose of the application in a real-time framework would be to minimize the flood damages at Nashville, Tennessee by keeping the flood stages under the 100-year flood stage. This application also compared the three unsteady flow simulation scenarios: one-dimensional, two-dimensional and combined one- and two-dimensional unsteady flow.
ContributorsAlbo-Salih, Hasan Hadi Kraidi (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2019
Description
In the recent past, Iraq was considered relatively rich considering its water resources compared to its surroundings. Currently, the magnitude of water resource shortages in Iraq represents an important factor in the stability of the country and in protecting sustained economic development. The need for a practical, applicable, and sustainable river basin management for the Tigris and Euphrates Rivers in Iraq is essential. Applicable water resources allocation scenarios are important to minimize the potential future water crises in connection with water quality and quantity. The allocation of the available fresh water resources in addition to reclaimed water to different users in a sustainable manner is of the urgent necessities to maintain good water quantity and quality.
In this dissertation, predictive water allocation optimization models were developed which can be used to easily identify good alternatives for water management that can then be discussed, debated, adjusted, and simulated in greater detail. This study provides guidance for decision makers in Iraq for potential future conditions, where water supplies are reduced, and demonstrates how it is feasible to adopt an efficient water allocation strategy with flexibility in providing equitable water resource allocation considering alternative resource. Using reclaimed water will help in reducing the potential negative environmental impacts of treated or/and partially treated wastewater discharges while increasing the potential uses of reclaimed water for agriculture and other applications. Using reclaimed water for irrigation is logical and efficient to enhance the economy of farmers and the environment while providing a diversity of crops, especially since most of Iraq’s built or under construction wastewater treatment plants are located in or adjacent to agricultural lands. Adopting an optimization modelling approach can assist decision makers, ensuring their decisions will benefit the economy by incorporating global experiences to control water allocations in Iraq especially considering diminished water supplies.
In this dissertation, predictive water allocation optimization models were developed which can be used to easily identify good alternatives for water management that can then be discussed, debated, adjusted, and simulated in greater detail. This study provides guidance for decision makers in Iraq for potential future conditions, where water supplies are reduced, and demonstrates how it is feasible to adopt an efficient water allocation strategy with flexibility in providing equitable water resource allocation considering alternative resource. Using reclaimed water will help in reducing the potential negative environmental impacts of treated or/and partially treated wastewater discharges while increasing the potential uses of reclaimed water for agriculture and other applications. Using reclaimed water for irrigation is logical and efficient to enhance the economy of farmers and the environment while providing a diversity of crops, especially since most of Iraq’s built or under construction wastewater treatment plants are located in or adjacent to agricultural lands. Adopting an optimization modelling approach can assist decision makers, ensuring their decisions will benefit the economy by incorporating global experiences to control water allocations in Iraq especially considering diminished water supplies.
ContributorsAhmed, Ahmed Abdulrazzaq (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Thesis advisor) / Mascaro, Giuseppe (Committee member) / Muenich, Rebecca (Committee member) / Arizona State University (Publisher)
Created2019
Description
One of the two objectives of this dissertation is an investigation into the possible correlation between rainfall events and increased levels of E. coli and Mycobacterium using an existing data set. The literature states that levels of microbial concentrations do increase after rainfall events, but there are no studies to indicate this correlation applies in any Arizona water systems. The data analyzed for the bacterial concentrations project suggested the possibility of a correlation along one river but it is not conclusive to state that any correlation exists between rainfall events and the microbial concentration for many other sites included in the analysis. This is most likely due to the highly engineered water delivery systems that are not directly impacted.
The secondary objective was to determine if there are environmental variables collected from an ongoing project which would be a good candidate for making predictions about any of the project data parameters. Of the 79 possible opportunities for the model to accurately predict the dependent variable, it showed strong statistical favorability as well as experimentally favorable results towards Dissolved Organic Carbon as the best dependent variable from the data set, resulting in an accuracy of 41%. This is relevant since Dissolved Organic Carbon is one of the most important water quality parameters of concern for drinking water treatment plants where disinfection by-products are a limiting factor. The need for further analysis and additional data collection is an obvious result from both studies. The use of hydrograph data instead of rainfall would be a logical new direction for the heavily engineered water delivery systems.
The secondary objective was to determine if there are environmental variables collected from an ongoing project which would be a good candidate for making predictions about any of the project data parameters. Of the 79 possible opportunities for the model to accurately predict the dependent variable, it showed strong statistical favorability as well as experimentally favorable results towards Dissolved Organic Carbon as the best dependent variable from the data set, resulting in an accuracy of 41%. This is relevant since Dissolved Organic Carbon is one of the most important water quality parameters of concern for drinking water treatment plants where disinfection by-products are a limiting factor. The need for further analysis and additional data collection is an obvious result from both studies. The use of hydrograph data instead of rainfall would be a logical new direction for the heavily engineered water delivery systems.
ContributorsBuell, Andrew (Author) / Fox, Peter (Thesis advisor) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Arizona State University (Publisher)
Created2018
Description
The need for rapid, specific and sensitive assays that provide a detection of bacterial indicators are important for monitoring water quality. Rapid detection using biosensor is a novel approach for microbiological testing applications. Besides, validation of rapid methods is an obstacle in adoption of such new bio-sensing technologies. In this study, the strategy developed is based on using the compound 4-methylumbelliferyl glucuronide (MUG), which is hydrolyzed rapidly by the action of E. coli β-D-glucuronidase (GUD) enzyme to yield a fluorogenic product that can be quantified and directly related to the number of E. coli cells present in water samples. The detection time required for the biosensor response ranged from 30 to 120 minutes, depending on the number of bacteria. The specificity of the MUG based biosensor platform assay for the detection of E. coli was examined by pure cultures of non-target bacterial genera and also non-target substrates. GUD activity was found to be specific for E. coli and no such enzymatic activity was detected in other species. Moreover, the sensitivity of rapid enzymatic assays was investigated and repeatedly determined to be less than 10 E. coli cells per reaction vial concentrated from 100 mL of water samples. The applicability of the method was tested by performing fluorescence assays under pure and mixed bacterial flora in environmental samples. In addition, the procedural QA/QC for routine monitoring of drinking water samples have been validated by comparing the performance of the biosensor platform for the detection of E. coli and culture-based standard techniques such as Membrane Filtration (MF). The results of this study indicated that the fluorescence signals generated in samples using specific substrate molecules can be utilized to develop a bio-sensing platform for the detection of E. coli in drinking water. The procedural QA/QC of the biosensor will provide both industry and regulatory authorities a useful tool for near real-time monitoring of E. coli in drinking water samples. Furthermore, this system can be applied independently or in conjunction with other methods as a part of an array of biochemical assays in order to reliably detect E. coli in water.
ContributorsHesari, Nikou (Author) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Fox, Peter (Committee member) / Stout, Valerie (Committee member) / Arizona State University (Publisher)
Created2015
Description
Carbon dioxide (CO2) is one of the most dangerous greenhouse gas. Its concentration in the atmosphere has increased to very high levels since the industrial revolution. This continues to be a threat due to increasing energy demands. 60% of the worlds global emissions come from automobiles and other such moving sources. Hence, to stay within safe limits, it is extremely important to curb current emissions and remove those which have already been emitted. Out of many available technologies, one such technology is the moisture swing based air capture technology that makes use of resin material that absorbs CO2 when it is dry and releases it when it is wet. A mathematical model was developed to better understand the mechanism of this process. In order to validate this model, numerical simulation and experimentation was done. Once the mechanism was proved, it was seen that there are many factors and parameters that govern this process. Some of these do not have definite value. To find the best fit value for these parameters, an optimized fitting routine needs to be developed that can minimize the standard deviation of the error. This thesis looks into ways in which the optimization of parameters can be done and the possible future work by using substantial data.
ContributorsChopra, Vinuta (Author) / Lackner, Klaus S (Thesis advisor) / Fox, Peter (Committee member) / Wright, Allen (Committee member) / Arizona State University (Publisher)
Created2016
Description
Bioretention basins are a common stormwater best management practice (BMP) used to mitigate the hydrologic consequences of urbanization. Dry wells, also known as vadose-zone wells, have been used extensively in bioretention basins in Maricopa County, Arizona to decrease total drain time and recharge groundwater. A mixed integer nonlinear programming (MINLP) model has been developed for the minimum cost design of bioretention basins with dry wells.
The model developed simultaneously determines the peak stormwater inflow from watershed parameters and optimizes the size of the basin and the number and depth of dry wells based on infiltration, evapotranspiration (ET), and dry well characteristics and cost inputs. The modified rational method is used for the design storm hydrograph, and the Green-Ampt method is used for infiltration. ET rates are calculated using the Penman Monteith method or the Hargreaves-Samani method. The dry well flow rate is determined using an equation developed for reverse auger-hole flow.
The first phase of development of the model is to expand a nonlinear programming (NLP) for the optimal design of infiltration basins for use with bioretention basins. Next a single dry well is added to the NLP bioretention basin optimization model. Finally the number of dry wells in the basin is modeled as an integer variable creating a MINLP problem. The NLP models and MINLP model are solved using the General Algebraic Modeling System (GAMS). Two example applications demonstrate the efficiency and practicality of the model.
The model developed simultaneously determines the peak stormwater inflow from watershed parameters and optimizes the size of the basin and the number and depth of dry wells based on infiltration, evapotranspiration (ET), and dry well characteristics and cost inputs. The modified rational method is used for the design storm hydrograph, and the Green-Ampt method is used for infiltration. ET rates are calculated using the Penman Monteith method or the Hargreaves-Samani method. The dry well flow rate is determined using an equation developed for reverse auger-hole flow.
The first phase of development of the model is to expand a nonlinear programming (NLP) for the optimal design of infiltration basins for use with bioretention basins. Next a single dry well is added to the NLP bioretention basin optimization model. Finally the number of dry wells in the basin is modeled as an integer variable creating a MINLP problem. The NLP models and MINLP model are solved using the General Algebraic Modeling System (GAMS). Two example applications demonstrate the efficiency and practicality of the model.
ContributorsLacy, Mason (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Wang, Zhihua (Committee member) / Arizona State University (Publisher)
Created2016
Description
Vegetative filter strips (VFS) are an effective methodology used for storm water management particularly for large urban parking lots. An optimization model for the design of vegetative filter strips that minimizes the amount of land required for stormwater management using the VFS is developed in this study. The resulting optimization model is based upon the kinematic wave equation for overland sheet flow along with equations defining the cumulative infiltration and infiltration rate.
In addition to the stormwater management function, Vegetative filter strips (VFS) are effective mechanisms for control of sediment flow and soil erosion from agricultural and urban lands. Erosion is a major problem associated with areas subjected to high runoffs or steep slopes across the globe. In order to effect economy in the design of grass filter strips as a mechanism for sediment control & stormwater management, an optimization model is required that minimizes the land requirements for the VFS. The optimization model presented in this study includes an intricate system of equations including the equations defining the sheet flow on the paved and grassed area combined with the equations defining the sediment transport over the vegetative filter strip using a non-linear programming optimization model. In this study, the optimization model has been applied using a sensitivity analysis of parameters such as different soil types, rainfall characteristics etc., performed to validate the model
In addition to the stormwater management function, Vegetative filter strips (VFS) are effective mechanisms for control of sediment flow and soil erosion from agricultural and urban lands. Erosion is a major problem associated with areas subjected to high runoffs or steep slopes across the globe. In order to effect economy in the design of grass filter strips as a mechanism for sediment control & stormwater management, an optimization model is required that minimizes the land requirements for the VFS. The optimization model presented in this study includes an intricate system of equations including the equations defining the sheet flow on the paved and grassed area combined with the equations defining the sediment transport over the vegetative filter strip using a non-linear programming optimization model. In this study, the optimization model has been applied using a sensitivity analysis of parameters such as different soil types, rainfall characteristics etc., performed to validate the model
ContributorsKhatavkar, Puneet N (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Wang, Zhihua (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2015
Description
This dissertation investigates the mechanisms that lead to fouling, as well as how an understanding of how these mechanisms can be leveraged to mitigate fouling.
To limit fouling on feed spacers, various coatings were applied. The results showed silver-coated biocidal spacers outperformed other spacers by all measures. The control polypropylene spacers performed in-line with, or better than, the other coatings. Polypropylene’s relative anti-adhesiveness is due to its surface free energy (SFE; 30.0 +/- 2.8 mN/m), which, according to previously generated models, is near the ideal SFE for resisting adhesion of bacteria and organics (~25 mN/m).
Previous research has indicated that electrochemical surfaces can be used to remove biofilms. To better elucidate the conditions and kinetics of biofilm removal, optical coherence tomography microscopy was used to visualize the biofouling and subsequent cleaning of the surface. The 50.0 mA cm-2 and 87.5 mA cm-2 current densities proved most effective in removing the biofilm. The 50.0 mA cm-2 condition offers the best balance between performance and energy use for anodic operation.
To test the potential to incorporate electrochemical coatings into infrastructure, membranes were coated with carbon nanotubes (CNTs), rendering the membranes electrochemically active. These membranes were biofouled and subsequently cleaned via electrochemical reactions. P. aeruginosa was given 72h to develop a biofilm on the CNT-coated membranes in a synthetic medium simulating desalination brines. Cathodic reactions, which generate H2 gas, produce vigorous bubbling at a current density of 12.5 mA cm-2 and higher, leading to a rapid and complete displacement of the biofilm from the CNT-functionalized membrane surface. In comparison, anodic reactions were unable to disperse the biofilms from the surface at similar current densities.
The scaling behavior of a nanophotonics-enabled solar membrane distillation (NESMD) system was investigated. The results showed the NESMD system to be resistant to scaling. The system operated without any decline in flux up to concentrations 6x higher than the initial salt concentration (8,439 mg/L), whereas in traditional membrane distillation (MD), flux essentially stopped at a salt concentration factor of 2x. Microscope and analytical analyses showed more fouling on the membranes from the MD system.
To limit fouling on feed spacers, various coatings were applied. The results showed silver-coated biocidal spacers outperformed other spacers by all measures. The control polypropylene spacers performed in-line with, or better than, the other coatings. Polypropylene’s relative anti-adhesiveness is due to its surface free energy (SFE; 30.0 +/- 2.8 mN/m), which, according to previously generated models, is near the ideal SFE for resisting adhesion of bacteria and organics (~25 mN/m).
Previous research has indicated that electrochemical surfaces can be used to remove biofilms. To better elucidate the conditions and kinetics of biofilm removal, optical coherence tomography microscopy was used to visualize the biofouling and subsequent cleaning of the surface. The 50.0 mA cm-2 and 87.5 mA cm-2 current densities proved most effective in removing the biofilm. The 50.0 mA cm-2 condition offers the best balance between performance and energy use for anodic operation.
To test the potential to incorporate electrochemical coatings into infrastructure, membranes were coated with carbon nanotubes (CNTs), rendering the membranes electrochemically active. These membranes were biofouled and subsequently cleaned via electrochemical reactions. P. aeruginosa was given 72h to develop a biofilm on the CNT-coated membranes in a synthetic medium simulating desalination brines. Cathodic reactions, which generate H2 gas, produce vigorous bubbling at a current density of 12.5 mA cm-2 and higher, leading to a rapid and complete displacement of the biofilm from the CNT-functionalized membrane surface. In comparison, anodic reactions were unable to disperse the biofilms from the surface at similar current densities.
The scaling behavior of a nanophotonics-enabled solar membrane distillation (NESMD) system was investigated. The results showed the NESMD system to be resistant to scaling. The system operated without any decline in flux up to concentrations 6x higher than the initial salt concentration (8,439 mg/L), whereas in traditional membrane distillation (MD), flux essentially stopped at a salt concentration factor of 2x. Microscope and analytical analyses showed more fouling on the membranes from the MD system.
ContributorsRice, Douglas, Ph.D (Author) / Perreault, Francois (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Fox, Peter (Committee member) / Lind-Thomas, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2019