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Characterization of DOC in "Accidental" Urban Wetlands in Phoenix, AZ

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Accidental wetlands have been created on the bed of the Salt River and are fed by storm-water outfalls discharging at various sections of the Phoenix Metropolitan Area. Water discharges from these outfalls throughout the year, during both dry conditions (base

Accidental wetlands have been created on the bed of the Salt River and are fed by storm-water outfalls discharging at various sections of the Phoenix Metropolitan Area. Water discharges from these outfalls throughout the year, during both dry conditions (base flow) and during rain events (storm flow). In this study, DOC content and composition was studied during these two flow conditions, in the outfalls and along the wetland flow path. The importance of DOC lies in its role in transporting carbon via water movement, between different parts of a landscape, and therefore between pools in the ecosystem. Urbanization has influenced content and composition of DOC entering the accidental urban wetland via outfalls as they represent watersheds from different areas in Phoenix. First, DOC load exhibited higher quantities during stormflow compared to baseflow conditions. Second, DOC load and fluorescence analysis outcomes concluded the outfalls are different from each other. The inputs of water on the north side of the channel represent City of Phoenix watersheds were similar to each other and had high DOC load. The northern outfalls are both different in load and composition from the outfall pipe on the southern bank of the wetland as it represents South Mountain watershed. Fluorescence analysis results also concluded compositional changes occurred along the wetland flow path during both stormflow and baseflow conditions. In this study, it was explored how urbanization and the associated changes in hydrology and geomorphology have affected a desert wetland's carbon content.

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2016-05

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Participatory roles of urban trees in regulating environmental quality

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The world has been continuously urbanized and is currently accommodating more than half of the human population. Despite that cities cover only less than 3% of the Earth’s land surface area, they emerged as hotspots of anthropogenic activities. The drastic

The world has been continuously urbanized and is currently accommodating more than half of the human population. Despite that cities cover only less than 3% of the Earth’s land surface area, they emerged as hotspots of anthropogenic activities. The drastic land use changes, complex three-dimensional urban terrain, and anthropogenic heat emissions alter the transport of mass, heat, and momentum, especially within the urban canopy layer. As a result, cities are confronting numerous environmental challenges such as exacerbated heat stress, frequent air pollution episodes, degraded water quality, increased energy consumption and water use, etc. Green infrastructure, in particular, the use of trees, has been proved as an effective means to improve urban environmental quality in existing research. However, quantitative evaluations of the efficacy of urban trees in regulating air quality and thermal environment are impeded by the limited temporal and spatial scales in field measurements and the deficiency in numerical models.

This dissertation aims to advance the simulation of realistic functions of urban trees in both microscale and mesoscale numerical models, and to systematically evaluate the cooling capacity of urban trees under thermal extremes. A coupled large-eddy simulation–Lagrangian stochastic modeling framework is developed for the complex urban environment and is used to evaluate the impact of urban trees on traffic-emitted pollutants. Results show that the model is robust for capturing the dispersion of urban air pollutants and how strategically implemented urban trees can reduce vehicle-emitted pollution. To evaluate the impact of urban trees on the thermal environment, the radiative shading effect of trees are incorporated into the integrated Weather Research and Forecasting model. The mesoscale model is used to simulate shade trees over the contiguous United States, suggesting how the efficacy of urban trees depends on geographical and climatic conditions. The cooling capacity of urban trees and its response to thermal extremes are then quantified for major metropolitans in the United States based on remotely sensed data. It is found the nonlinear temperature dependence of the cooling capacity remarkably resembles the thermodynamic liquid-water–vapor equilibrium. The findings in this dissertation are informative to evaluating and implementing urban trees, and green infrastructure in large, as an important urban planning strategy to cope with emergent global environmental changes.

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2019

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Analysis of uncertainty in water management and wastewater-based population health assessments

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Uncertainty is inherent in predictive decision-making, both with respect to forecasting plausible future conditions based on a historic record, and with respect to backcasting likely upstream states from downstream observations. In the first chapter, I evaluated the status of current

Uncertainty is inherent in predictive decision-making, both with respect to forecasting plausible future conditions based on a historic record, and with respect to backcasting likely upstream states from downstream observations. In the first chapter, I evaluated the status of current water resources management policy in the United States (U.S.) with respect to its integration of projective uncertainty into state-level flooding, drought, supply and demand, and climate guidance. I found uncertainty largely absent and discussed only qualitatively rather than quantitatively. In the second chapter, I turned to uncertainty in the interpretation of downstream observations as indicators of upstream behaviors in the field of Wastewater-Based Epidemiology (WBE), which has made possible the near real-time, yet anonymous, monitoring of public health via measurements of biomarkers excreted to wastewater. I found globally, seasonality of air and soil temperature causes biomarker degradation to vary up to 13-fold over the course of a year, constituting part of the background processes WBE must address, or detrend, prior to decision-making. To determine whether the seasonal change in degradation rates was introducing previously unaccounted for uncertainty with respect to differences in observed summertime and winter-time populations, I evaluated demographic indicators recorded by the Census Bureau for correlation with their distance from all major wastewater treatment plants across the U.S. The analysis identified statistically significant correlation for household income, education attainment, unemployment, military service, and the absence of health insurance. Finally, the model was applied to a city-wide case study to test whether temperature could explain some of the trends observed in monthly observations of two opiate compounds. Modeling suggests some of the monthly changes were attributed to natural temperature fluctuation rather than to trends in the substances’ consumption, and that uncertainty regarding discharge location can dominate even relative observed differences in opiate detections. In summary, my work has found temperature an important modulator of WBE results, influencing both the type of populations observed and the likelihood of upstream behaviors disproportionally magnified or obscured, particularly for the more labile biomarkers. There exists significant potential for improving the understanding of empirical observations via numerical modeling and the application of spatial analysis tools.

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2019

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Improvement in convective precipitation and land surface prediction over complex terrain

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Land surface fluxes of energy and mass developed over heterogeneous mountain landscapes are fundamental to atmospheric processes. However, due to their high complexity and the lack of spatial observations, land surface processes and land-atmosphere interactions are not fully understood in

Land surface fluxes of energy and mass developed over heterogeneous mountain landscapes are fundamental to atmospheric processes. However, due to their high complexity and the lack of spatial observations, land surface processes and land-atmosphere interactions are not fully understood in mountain regions. This thesis investigates land surface processes and their impact on convective precipitation by conducting numerical modeling experiments at multiple scales over the North American Monsoon (NAM) region. Specifically, the following scientific questions are addressed: (1) how do land surface conditions evolve during the monsoon season, and what are their main controls?, (2) how do the diurnal cycles of surface energy fluxes vary during the monsoon season for the major ecosystems?, and (3) what are the impacts of surface soil moisture and vegetation condition on convective precipitation?

Hydrologic simulation using the TIN-based Real-time Integrated Basin Simulator (tRIBS) is firstly carried out to examine the seasonal evolution of land surface conditions. Results reveal that the spatial heterogeneity of land surface temperature and soil moisture increases dramatically with the onset of monsoon, which is related to seasonal changes in topographic and vegetation controls. Similar results are found at regional basin scale using the uncoupled WRF-Hydro model. Meanwhile, the diurnal cycles of surface energy fluxes show large variation between the major ecosystems. Differences in both the peak magnitude and peak timing of plant transpiration induce mesoscale heterogeneity in land surface conditions. Lastly, this dissertation examines the upscale effect of land surface heterogeneity on atmospheric condition through fully-coupled WRF-Hydro simulations. A series of process-based experiments were conducted to identify the pathways of soil moisture-rainfall feedback mechanism over the NAM region. While modeling experiments confirm the existence of positive soil moisture/vegetation-rainfall feedback, their exact pathways are slightly different. Interactions between soil moisture, vegetation cover, and rainfall through a series of land surface and atmospheric boundary layer processes highlight the strong land-atmosphere coupling in the NAM region, and have important implications on convective rainfall prediction. Overall, this dissertation advances the study of complex land surface processes over the NAM region, and made important contributions in linking complex hydrologic, ecologic and atmospheric processes through numerical modeling.

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2016

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Urban microclimatic response to landscape changes via land-atmosphere interactions

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Rapid urban expansion and the associated landscape modifications have led to significant changes of surface processes in built environments. These changes further interact with the overlying atmospheric boundary layer and strongly modulate urban microclimate. To capture the impacts of urban

Rapid urban expansion and the associated landscape modifications have led to significant changes of surface processes in built environments. These changes further interact with the overlying atmospheric boundary layer and strongly modulate urban microclimate. To capture the impacts of urban land surface processes on urban boundary layer dynamics, a coupled urban land-atmospheric modeling framework has been developed. The urban land surface is parameterized by an advanced single-layer urban canopy model (SLUCM) with realistic representations of urban green infrastructures such as lawn, tree, and green roof, etc. The urban atmospheric boundary layer is simulated by a single column model (SCM) with both convective and stable schemes. This coupled SLUCM-SCM framework can simulate the time evolution and vertical profile of different meteorological variables such as virtual potential temperature, specific humidity and carbon dioxide concentration. The coupled framework has been calibrated and validated in the metropolitan Phoenix area, Arizona. To quantify the model sensitivity, an advanced stochastic approach based on Markov-Chain Monte Carlo procedure has been applied. It is found that the development of urban boundary layer is highly sensitive to surface characteristics of built terrains, including urban land use, geometry, roughness of momentum, and vegetation fraction. In particular, different types of urban vegetation (mesic/xeric) affect the boundary layer dynamics through different mechanisms. Furthermore, this framework can be implanted into large-scale models such as Weather Research and Forecasting model to assess the impact of urbanization on regional climate.

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2016

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Environmental releases of neonicotinoid and fipronil insecticides via U.S. wastewater infrastructure

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This dissertation is focused on environmental releases from U.S. wastewater infrastructure of recently introduced, mass-produced insecticides, namely neonicotinoids as well as fipronil and its major degradates (sulfone, sulfide, amide, and desulfinyl derivatives), jointly known as fiproles. Both groups of compounds

This dissertation is focused on environmental releases from U.S. wastewater infrastructure of recently introduced, mass-produced insecticides, namely neonicotinoids as well as fipronil and its major degradates (sulfone, sulfide, amide, and desulfinyl derivatives), jointly known as fiproles. Both groups of compounds recently have caught the attention of regulatory agencies worldwide due to their toxic effects on pollinators and on aquatic invertebrates at very low, part-per-trillion levels (Chapter 1). Mass balance studies conducted for 13 U.S. wastewater treatment plants (WWTPs) showed ubiquitous occurrence (3-666 ng/L) and persistence of neonicotinoids (Chapter 2). For the years 2001 through 2016, a longitudinal nationwide study was conducted on the occurrence of fiproles, via analysis of sludge as well as raw and treated wastewater samples. Sludge analysis revealed ubiquitous fiprole occurrence since 2001 (0.2-385 µg/kg dry weight) and a significant increase (2.4±0.3-fold; p<0.005) to elevated levels found both in 2006/7 and 2015/6. This study established a marked persistence of fiproles during both wastewater and sludge treatment, while also identifying non-agricultural uses as a major source of fiprole loading to wastewater (Chapter 3). Eight WWTPs were monitored in Northern California to assess pesticide inputs into San Francisco Bay from wastewater discharge. Per-capita-contaminant-loading calculations identified flea and tick control agents for use on pets as a previously underappreciated source term dominating the mass loading of insecticides to WWTPs in sewage and to the Bay in treated wastewater (Chapter 4). A nationwide assessment of fipronil emissions revealed that pet products, while representing only 22±7% of total fipronil usage (2011-2015), accounted for 86±5% of the mass loading to U.S. surface waters (Chapter 5). In summary, the root cause for considerable annual discharges into U.S. surface waters of the neonicotinoid imidacloprid (3,700-5,500 kg/y) and of fipronil related compounds (1,600-2,400 kg/y) is domestic rather than agricultural insecticide use. Reclaimed effluent from U.S. WWTPs contained insecticide levels that exceed toxicity benchmarks for sensitive aquatic invertebrates in 83% of cases for imidacloprid and in 67% of cases for fipronil. Recommendations are provided on how to limit toxic inputs in the future.

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2017

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Geochemical analysis of the leachate generated after zero valent metals addition to municipal solid waste

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Zero-Valent Metals (ZVM) are highly reactive materials and have been proved to be effective in contaminant reduction in soils and groundwater remediation. In fact, zero-Valent Iron (ZVI) has proven to be very effective in removing, particularly chlorinated organics, heavy metals,

Zero-Valent Metals (ZVM) are highly reactive materials and have been proved to be effective in contaminant reduction in soils and groundwater remediation. In fact, zero-Valent Iron (ZVI) has proven to be very effective in removing, particularly chlorinated organics, heavy metals, and odorous sulfides. Addition of ZVI has also been proved in enhancing the methane gas generation in anaerobic digestion of activated sludge. However, no studies have been conducted regarding the effect of ZVM stimulation to Municipal Solid Waste (MSW) degradation. Therefore, a collaborative study was developed to manipulate microbial activity in the landfill bioreactors to favor methane production by adding ZVMs. This study focuses on evaluating the effects of added ZVM on the leachate generated from replicated lab scale landfill bioreactors. The specific objective was to investigate the effects of ZVMs addition on the organic and inorganic pollutants in leachate. The hypothesis here evaluated was that adding ZVM including ZVI and Zero Valent Manganese (ZVMn) will enhance the removal rates of the organic pollutants present in the leachate, likely by a putative higher rate of microbial metabolism. Test with six (4.23 gallons) bioreactors assembled with MSW collected from the Salt River Landfill and Southwest Regional Landfill showed that under 5 grams /liter of ZVI and 0.625 grams/liter of ZVMn additions, no significant difference was observed in the pH and temperature data of the leachate generated from these reactors. The conductivity data suggested the steady rise across all reactors over the period of time. The removal efficiency of sCOD was highest (27.112 mg/lit/day) for the reactors added with ZVMn at the end of 150 days for bottom layer, however the removal rate was highest (16.955 mg/lit/day) for ZVI after the end of 150 days of the middle layer. Similar trends in the results was observed in TC analysis. HPLC study indicated the dominance of the concentration of heptanoate and isovalerate were leachate generated from the bottom layer across all reactors. Heptanoate continued to dominate in the ZVMn added leachate even after middle layer injection. IC analysis concluded the chloride was dominant in the leachate generated from all the reactors and there was a steady increase in the chloride content over the period of time. Along with chloride, fluoride, bromide, nitrate, nitrite, phosphate and sulfate were also detected in considerable concentrations. In the summary, the addition of the zero valent metals has proved to be efficient in removal of the organics present in the leachate.

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2019

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Evaluating the impact of land cover composition on water, energy, and carbon fluxes in urban and rangeland ecosystems of the southwestern United States

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Urbanization and woody plant encroachment, with subsequent brush management, are two significant land cover changes that are represented in the southwestern United States. Urban areas continue to grow, and rangelands are undergoing vegetation conversions, either purposely through various rangeland management

Urbanization and woody plant encroachment, with subsequent brush management, are two significant land cover changes that are represented in the southwestern United States. Urban areas continue to grow, and rangelands are undergoing vegetation conversions, either purposely through various rangeland management techniques, or by accident, through inadvertent effects of climate and management. This thesis investigates how areas undergoing land cover conversions in a semiarid region, through urbanization or rangeland management, influences energy, water and carbon fluxes. Specifically, the following scientific questions are addressed: (1) what is the impact of different urban land cover types in Phoenix, AZ on energy and water fluxes?, (2) how does the land cover heterogeneity influence energy, water, and carbon fluxes in a semiarid rangeland undergoing woody plant encroachment?, and (3) what is the impact of brush management on energy, water, and carbon fluxes?

The eddy covariance technique is well established to measure energy, water, and carbon fluxes and is used to quantify and compare flux measurements over different land surfaces. Results reveal that in an urban setting, paved surfaces exhibit the largest sensible and lowest latent heat fluxes in an urban environment, while a mesic landscape exhibits the largest latent heat fluxes, due to heavy irrigation. Irrigation impacts flux sensitivity to precipitation input, where latent heat fluxes increase with precipitation in xeric and parking lot landscapes, but do not impact the mesic system. In a semiarid managed rangeland, past management strategies and disturbance histories impact vegetation distribution, particularly the distribution of mesquite trees. At the site with less mesquite coverage, evapotranspiration (ET) is greater, due to greater grass cover. Both sites are generally net sinks of CO2, which is largely dependent on moisture availability, while the site with greater mesquite coverage has more respiration and generally greater gross ecosystem production (GEP). Initial impacts of brush management reveal ET and GEP decrease, due to the absence of mesquite trees. However the impact appears to be minimal by the end of the productive season. Overall, this dissertation advances the understanding of land cover change impacts on surface energy, water, and carbon fluxes in semiarid ecosystems.

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2017

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Tracking chemical indicators of public health in the urban water environment

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This dissertation focuses on the application of urban metabolism metrology (UMM) to process streams of the natural and built water environment to gauge public health concerning exposure to carcinogenic N-nitrosamines and abuse of narcotics. A survey of sources of exposure

This dissertation focuses on the application of urban metabolism metrology (UMM) to process streams of the natural and built water environment to gauge public health concerning exposure to carcinogenic N-nitrosamines and abuse of narcotics. A survey of sources of exposure to N-nitrosamines in the U.S. population identified contaminated food products (1,900 ± 380 ng/day) as important drivers of attributable cancer risk (Chapter 2). Freshwater sediments in the proximity of U.S. municipal wastewater treatment plants were shown for the first time to harbor carcinogenic N-nitrosamine congeners, including N-nitrosodibutylamine (0.2-3.3 ng/g dw), N-nitrosodiphenylamine (0.2-4.7 ng/g dw), and N-nitrosopyrrolidine (3.4-19.6 ng/g dw) were, with treated wastewater discharge representing one potential factor contributing to the observed contamination (p=0.42) (Chapter 3). Opioid abuse rates in two small midwestern communities were estimated through the application of wastewater-based epidemiology (WBE). Average concentrations of opioids (City 1; City 2) were highest for morphine (713 ± 38, 306 ± 29 ng/L) and varied by for the remainder of the screened analytes. Furthermore, concentrations of the powerful opioid fentanyl (1.7 ± 0.2, 1.0 ± 0.5 ng/L) in wastewater were reported for the first time in the literature for the U.S. (Chapter 4). To gauge narcotic consumption within college-aged adults the WBE process used in Chapter 4 was applied to wastewater collected from a large university in the Southwestern U.S. Estimated narcotics consumption, in units of mg/day/1,000 persons showed the following rank order: cocaine (470 ± 42), heroin (474 ± 32), amphetamine (302 ± 14) and methylphenidate (236 ± 28). Most parental drugs and their respective metabolites showed detection frequencies in campus wastewater of 80% or more, with the notable exception of fentanyl, norfentanyl, buprenorphine, and norbuprenorphine. Estimated consumption of all narcotics, aside from attention-deficit/hyperactivity disorder medication, were higher than values reported in previous U.S. WBE studies for U.S. campuses (Chapter 5). The analyses presented here have identified variation in narcotic consumption habits across different U.S. communities, which can be gauged through UMM. Application of these techniques should be implemented throughout U.S. communities to provide insight into ongoing substance abuse and health issues within a community.

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2018