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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,

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
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Description
The consumption of feedstocks from agriculture and forestry by current biofuel production has raised concerns about food security and land availability. In the meantime, intensive human activities have created a large amount of marginal lands that require management. This study investigated the viability of aligning land management with biofuel production

The consumption of feedstocks from agriculture and forestry by current biofuel production has raised concerns about food security and land availability. In the meantime, intensive human activities have created a large amount of marginal lands that require management. This study investigated the viability of aligning land management with biofuel production on marginal lands. Biofuel crop production on two types of marginal lands, namely urban vacant lots and abandoned mine lands (AMLs), were assessed. The investigation of biofuel production on urban marginal land was carried out in Pittsburgh between 2008 and 2011, using the sunflower gardens developed by a Pittsburgh non-profit as an example. Results showed that the crops from urban marginal lands were safe for biofuel. The crop yield was 20% of that on agricultural land while the low input agriculture was used in crop cultivation. The energy balance analysis demonstrated that the sunflower gardens could produce a net energy return even at the current low yield. Biofuel production on AML was assessed from experiments conducted in a greenhouse for sunflower, soybean, corn, canola and camelina. The research successfully created an industrial symbiosis by using bauxite as soil amendment to enable plant growth on very acidic mine refuse. Phytoremediation and soil amendments were found to be able to effectively reduce contamination in the AML and its runoff. Results from this research supported that biofuel production on marginal lands could be a unique and feasible option for cultivating biofuel feedstocks.
ContributorsZhao, Xi (Author) / Landis, Amy (Thesis advisor) / Fox, Peter (Committee member) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2013
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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

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
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Description
Ecolabels are the main driving force of consumer knowledge in the realm of sustainable product purchasing. While ecolabels strive to improve consumer's purchasing decisions, they have overwhelmed the market, leaving consumers confused and distrustful of what each label means. This study attempts to validate and understand environmental concerns commonly found

Ecolabels are the main driving force of consumer knowledge in the realm of sustainable product purchasing. While ecolabels strive to improve consumer's purchasing decisions, they have overwhelmed the market, leaving consumers confused and distrustful of what each label means. This study attempts to validate and understand environmental concerns commonly found in ecolabel criteria and the implications they have within the life cycle of a product. A life cycle assessment (LCA) case study of cosmetic products is used in comparison with current ecolabel program criteria to assess whether or not ecolabels are effectively driving environmental improvements in high impact areas throughout the life cycle of a product. Focus is placed on determining the general issues addressed by ecolabelling criteria and how these issues relate to hotspots derived through a practiced scientific methodology. Through this analysis, it was determined that a majority the top performing supply chain environmental impacts are covered, in some fashion, within ecolabelling criteria, but some, such as agricultural land occupation, are covered to a lesser extent or not at all. Additional criteria are suggested to fill the gaps found in ecolabelling programs and better address the environmental impacts most pertinent to the supply chain. Ecolabels have also been found to have a broader coverage then what can currently be addressed using LCA. The results of this analysis have led to a set of recommendations for furthering the integration between ecolabels and life cycle tools.
ContributorsBernardo, Melissa (Author) / Dooley, Kevin (Thesis advisor) / Chester, Mikhail (Thesis advisor) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Quagga Mussels (Dreissena bugensis) are an invasive species of mollusk that have established themselves within the Colorado River system of Arizona since 2007. However, despite close proximity and frequent travel by recreational boaters between reservoirs, they have not yet infested the Salt River or Verde River systems. Laboratory experimentation was

Quagga Mussels (Dreissena bugensis) are an invasive species of mollusk that have established themselves within the Colorado River system of Arizona since 2007. However, despite close proximity and frequent travel by recreational boaters between reservoirs, they have not yet infested the Salt River or Verde River systems. Laboratory experimentation was done to test the survival rate of adult D. bugensis specimens in waters collected from Bartlett Lake (Verde River), Saguaro Lake (Salt River), and Salt River Project (SRP) canals (Salt River/Verde River/Colorado River blend) as well as Central Arizona Project (CAP) canals with the addition of turbidity to simulate high runoff storm events. Under each condition, adult survival for a time period of 21 days exceeded 98%, ruling out water chemistry or turbidity as a factor. Spawning was investigated using mussels collected from Lake Pleasant in August 2015. In 4 trials of serotonin dosage between 0.5 – 1.0 mMol, spawning was not successful. Calanoid copepod predation was also investigated by field sampling at Lake Pleasant, Saguaro Lake, and Bartlett Lake during September 2015. Calanoid copepods were identified in Lake Pleasant at a density of 104.22 individuals per cubic meter at a depth of 2 meters and 9.75 individuals per cubic meter at the surface. Calanoid copepods were not found in Bartlett Lake or Saguaro Lake, ruling out copepod predation as a factor. Finally, dissolved oxygen and temperature trends were analyzed in each reservoir. While temperature profiles are similar throughout the year, seasonal drops in dissolved oxygen below survivable concentrations for D. bugensis has been observed in both Saguaro Lake and Bartlett Lake but not Lake Pleasant, representing the most plausible explanation for no observed infestation.
ContributorsSokolowski, Matthew (Author) / Fox, Peter (Thesis advisor) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Arizona State University (Publisher)
Created2015
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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

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