Matching Items (73)

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Coupled Abiotic and Biotic Cycling of Nitrous Oxide

Description

Nitrous oxide (N2O) is an important greenhouse gas and an oxidant respired by a

diverse range of anaerobic microbes, but its sources and sinks are poorly understood. The overarching goal of

Nitrous oxide (N2O) is an important greenhouse gas and an oxidant respired by a

diverse range of anaerobic microbes, but its sources and sinks are poorly understood. The overarching goal of my dissertation is to explore abiotic N2O formation and microbial N2O consumption across reducing environments of the early and modern Earth. By combining experiments as well as diffusion and atmospheric modeling, I present evidence that N2O production can be catalyzed on iron mineral surfaces that may have been present in shallow waters of the Archean ocean. Using photochemical models, I showed that tropospheric N2O concentrations close to modern ones (ppb range) were possible before O2 accumulated. In peatlands of the Amazon basin (modern Earth), unexpected abiotic activity became apparent under anoxic conditions. However, care has to be taken to adequately disentangle abiotic from biotic reactions. I identified significant sterilant-induced changes in Fe2+ and dissolved organic matter pools (determined by fluorescence spectroscopy). Among all chemical and physical sterilants tested, γ - irradiation showed the least effect on reactant pools. Targeting geochemically diverse peatlands across Central and South America, I present evidence that coupled abiotic and biotic cycling of N2O could be a widespread phenomenon. Using isotopic tracers in the field, I showed that abiotic N2O fluxes rival biotic ones under in-situ conditions. Moreover, once N2O is produced, it is rapidly consumed by N2O-reducing microbes. Using amplicon sequencing and metagenomics, I demonstrated that this surprising N2O sink potential is associated with diverse bacteria, including the recently discovered clade II that is present in high proportions at Amazonian sites based on nosZ quantities. Finally, to evaluate the impact of nitrogen oxides on methane production in peatlands, I characterized soil nitrite (NO2–) and N2O abundances along soil profiles. I complemented field analyses with molecular work by deploying amplicon-based 16S rRNA and mcrA sequencing. The diversity and activity of soil methanogens was affected by the presence of NO2– and N2O, suggesting that methane emissions could be influenced by N2O cycling dynamics. Overall, my work proposes a key role for N2O in Earth systems across time and a central position in tropical microbial ecosystems.

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  • 2020

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Knowledge System Innovation for Resilient Coastal Cities

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Cities are in need of radical knowledge system innovations and designs in the age of the Anthropocene. Cities are complex sites of interactions across social, ecological, and technological dimensions. Cities

Cities are in need of radical knowledge system innovations and designs in the age of the Anthropocene. Cities are complex sites of interactions across social, ecological, and technological dimensions. Cities are also experiencing rapidly changing and intractable environmental conditions. Given uncertain and incomplete knowledge of both future environmental conditions and the outcomes of urban resilience efforts, today’s knowledge systems are unequipped to generate the knowledge and wisdom needed to act. As such, cities must modernize the knowledge infrastructure underpinning today’s complex urban systems. The principal objective of this dissertation is to make the case for, and guide, the vital knowledge system innovations that coastal cities need in order to build more resilient urban futures. Chapter 2 demonstrates the use of knowledge systems analysis as a tool to stress-test and upgrade the Federal Emergency Management Agency flood mapping knowledge system that drives flood resilience planning and decision-making in New York City. In Chapter 3, a conceptual framework is constructed for the design and analysis of knowledge co-production by integrating concepts across the co-production and urban social-ecological-technological systems literatures. In Chapter 4, the conceptual framework is used to analyze two case studies of knowledge co-production in the Miami Metropolitan Area to better inform decisions for how and when to employ co-production as a tool to achieve sustainability and resilience outcomes. In Chapter 5, six propositions are presented – derived from a synthesis of the literature and the three empirical cases – that knowledge professionals can employ to create, facilitate, and scale up knowledge system innovations: flatten knowledge hierarchies; create plural and positive visions of the future; construct knowledge co-production to achieve desired outcomes; acknowledge and anticipate the influence of power and authority; build anticipatory capacities to act under deep uncertainty; and identify and invest in knowledge innovations. While these six propositions apply to the context of coastal cities and flood resilience, most can also be useful to facilitate knowledge innovations to adapt to other complex and intractable environmental problems. Cities must move swiftly to create and catalyze knowledge system innovations given the scale of climate impacts and rapidly changing environmental conditions.

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  • 2020

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Spatiotemporal patterns, monitoring network design, and environmental justice of air pollution in the Phoenix metropolitan region: a landscape approach

Description

Air pollution is a serious problem in most urban areas around the world, which has a number of negative ecological and human health impacts. As a result, it's vitally important

Air pollution is a serious problem in most urban areas around the world, which has a number of negative ecological and human health impacts. As a result, it's vitally important to detect and characterize air pollutants to protect the health of the urban environment and our citizens. An important early step in this process is ensuring that the air pollution monitoring network is properly designed to capture the patterns of pollution and that all social demographics in the urban population are represented. An important aspect in characterizing air pollution patterns is scale in space and time which, along with pattern and process relationships, is a key subject in the field of landscape ecology. Thus, using multiple landscape ecological methods, this dissertation research begins by characterizing and quantifying the multi-scalar patterns of ozone (O3) and particulate matter (PM10) in the Phoenix, Arizona, metropolitan region. Results showed that pollution patterns are scale-dependent, O3 is a regionally-scaled pollutant at longer temporal scales, and PM10 is a locally-scaled pollutant with patterns sensitive to season. Next, this dissertation examines the monitoring network within Maricopa County. Using a novel multiscale indicator-based approach, the adequacy of the network was quantified by integrating inputs from various academic and government stakeholders. Furthermore, deficiencies were spatially defined and recommendations were made on how to strengthen the design of the network. A sustainability ranking system also provided new insight into the strengths and weaknesses of the network. Lastly, the study addresses the question of whether distinct social groups were experiencing inequitable exposure to pollutants - a key issue of distributive environmental injustice. A novel interdisciplinary method using multi-scalar ambient pollution data and hierarchical multiple regression models revealed environmental inequities between air pollutants and race, ethnicity, age, and socioeconomic classes. The results indicate that changing the scale of the analysis can change the equitable relationship between pollution and demographics. The scientific findings of the scale-dependent relationships among air pollution patterns, network design, and population demographics, brought to light through this study, can help policymakers make informed decisions for protecting the human health and the urban environment in the Phoenix metropolitan region and beyond.

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Date Created
  • 2014

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Direct and indirect ecological consequences of human activities in urban and native ecosystems

Description

Though cities occupy only a small percentage of Earth's terrestrial surface, humans concentrated in urban areas impact ecosystems at local, regional and global scales. I examined the direct and

Though cities occupy only a small percentage of Earth's terrestrial surface, humans concentrated in urban areas impact ecosystems at local, regional and global scales. I examined the direct and indirect ecological outcomes of human activities on both managed landscapes and protected native ecosystems in and around cities. First, I used highly managed residential yards, which compose nearly half of the heterogeneous urban land area, as a model system to examine the ecological effects of people's management choices and the social drivers of those decisions. I found that a complex set of individual and institutional social characteristics drives people's decisions, which in turn affect ecological structure and function across scales from yards to cities. This work demonstrates the link between individuals' decision-making and ecosystem service provisioning in highly managed urban ecosystems.

Second, I examined the distribution of urban-generated air pollutants and their complex ecological outcomes in protected native ecosystems. Atmospheric carbon dioxide (CO2), reactive nitrogen (N), and ozone (O3) are elevated near human activities and act as both resources and stressors to primary producers, but little is known about their co-occurring distribution or combined impacts on ecosystems. I investigated the urban "ecological airshed," including the spatial and temporal extent of N deposition, as well as CO2 and O3 concentrations in native preserves in Phoenix, Arizona and the outlying Sonoran Desert. I found elevated concentrations of ecologically relevant pollutants co-occur in both urban and remote native lands at levels that are likely to affect ecosystem structure and function. Finally, I tested the combined effects of CO2, N, and O3 on the dominant native and non-native herbaceous desert species in a multi-factor dose-response greenhouse experiment. Under current and predicted future air quality conditions, the non-native species (Schismus arabicus) had net positive growth despite physiological stress under high O3 concentrations. In contrast, the native species (Pectocarya recurvata) was more sensitive to O3 and, unlike the non-native species, did not benefit from the protective role of CO2. These results highlight the vulnerability of native ecosystems to current and future air pollution over the long term. Together, my research provides empirical evidence for future policies addressing multiple stressors in urban managed and native landscapes.

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Date Created
  • 2014

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Hydrothermal organic reduction and deoxygenation

Description

Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction

Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction pathways involving organic compounds under geochemically relevant hydrothermal conditions have now been characterized, but their mechanisms, in particular those involving mineral surface catalysis, are largely unknown. The overall goal of this work is to describe these mechanisms so that predictive models of reactivity can be developed and so that applications of these reactions beyond geochemistry can be explored. The focus of this dissertation is the mechanisms of hydrothermal dehydration and catalytic hydrogenation reactions. Kinetic and structure/activity relationships show that elimination occurs mainly by the E1 mechanism for simple alcohols via homogeneous catalysis. Stereochemical probes show that hydrogenation on nickel occurs on the metal surface. By combining dehydration with and catalytic reduction, effective deoxygenation of organic structures with various functional groups such as alkenes, polyols, ketones, and carboxylic acids can be accomplished under hydrothermal conditions, using either nickel or copper-zinc alloy. These geomimetic reactions can potentially be used in biomass reduction to generate useful fuels and other high value chemicals. Through the use of earth-abundant metal catalysts, and water as the solvent, the reactions presented in this dissertation are a green alternative to current biomass deoxygenation/reduction methods, which often use exotic, rare-metal catalysts, and organic solvents.

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Date Created
  • 2018

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Modeling the effect of urbanization on climate and dust generation over desert cities

Description

Understanding and predicting climate changes at the urban scale have been an important yet challenging problem in environmental engineering. The lack of reliable long-term observations at the urban scale makes

Understanding and predicting climate changes at the urban scale have been an important yet challenging problem in environmental engineering. The lack of reliable long-term observations at the urban scale makes it difficult to even assess past climate changes. Numerical modeling plays an important role in filling the gap of observation and predicting future changes. Numerical studies on the climatic effect of desert urbanization have focused on basic meteorological fields such as temperature and wind. For desert cities, urban expansion can lead to substantial changes in the local production of wind-blown dust, which have implications for air quality and public health. This study expands the existing framework of numerical simulation for desert urbanization to include the computation of dust generation related to urban land-use changes. This is accomplished by connecting a suite of numerical models, including a meso-scale meteorological model, a land-surface model, an urban canopy model, and a turbulence model, to produce the key parameters that control the surface fluxes of wind-blown dust. Those models generate the near-surface turbulence intensity, soil moisture, and land-surface properties, which are used to determine the dust fluxes from a set of laboratory-based empirical formulas. This framework is applied to a series of simulations for the desert city of Erbil across a period of rapid urbanization. The changes in surface dust fluxes associated with urbanization are quantified. An analysis of the model output further reveals the dependence of surface dust fluxes on local meteorological conditions. Future applications of the models to environmental prediction are discussed.

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Date Created
  • 2019

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Sources and Decomposition of Dissolved Organic Matter in Desert Streams

Description

Dissolved organic matter (DOM) is an important part of aquatic foodwebs because it contains carbon, nitrogen, and other elements required by heterotrophic organisms. It has many sources that determine its

Dissolved organic matter (DOM) is an important part of aquatic foodwebs because it contains carbon, nitrogen, and other elements required by heterotrophic organisms. It has many sources that determine its molecular composition, nutrient content, and biological lability and in turn, influence whether it is retained and processed in the stream reach or exported downstream. I examined the composition of DOM from vascular wetland plants, filamentous algae, and riparian tree leaf litter in Sonoran Desert streams and its decomposition by stream microbes. I used a combination of field observations, in-situ experiments, and a manipulative laboratory incubation to test (1) how dominant primary producers influence DOM chemical composition and ecosystem metabolism at the reach scale and (2) how DOM composition and nitrogen (N) content control microbial decomposition and stream uptake of DOM. I found that differences in streamwater DOM composition between two distinct reaches of Sycamore Creek did not affect in-situ stream respiration and gross primary production rates. Stream sediment microbial respiration rates did not differ significantly when incubated in the laboratory with DOM from wetland plants, algae, and leaf litter, thus all sources were similarly labile. However, whole-stream uptake of DOM increased from leaf to algal to wetland plant leachate. Desert streams have the potential to process DOM from leaf, wetland, and algal sources, though algal and wetland DOM, due to their more labile composition, can be more readily retained and mineralized.

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Date Created
  • 2018

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Monitoring algal abundance and water quality in Arizona reservoirs through field sampling and remote sensing

Description

Safe, readily available, and reliable sources of water are an essential component of any municipality’s infrastructure. Phoenix, Arizona, a southwestern city, has among the highest per capita water use in

Safe, readily available, and reliable sources of water are an essential component of any municipality’s infrastructure. Phoenix, Arizona, a southwestern city, has among the highest per capita water use in the United States, making it essential to carefully manage its reservoirs. Generally, municipal water bodies are monitored through field sampling. However, this approach is limited spatially and temporally in addition to being costly. In this study, the application of remotely sensed reflectance data from Landsat 7’s Enhanced Thematic Mapper Plus (ETM+) and Landsat 8’s Operational Land Imager (OLI) along with data generated through field-sampling is used to gain a better understanding of the seasonal development of algal communities and levels of suspended particulates in the three main terminal reservoirs supplying water to the Phoenix metro area: Bartlett Lake, Lake Pleasant, and Saguaro Lake. Algal abundances, particularly the abundance of filamentous cyanobacteria, increased with warmer temperatures in all three reservoirs and reached the highest comparative abundance in Bartlett Lake. Prymnesiophytes (the class of algae to which the toxin-producing golden algae belong) tended to peak between June and August, with one notable peak occurring in Saguaro Lake in August 2017 during which time a fish-kill was observed. In the cooler months algal abundance was comparatively lower in all three lakes, with a more even distribution of abundance across algae classes. In-situ data from March 2017 to March 2018 were compared with algal communities sampled approximately ten years ago in each reservoir to understand any possible long-term changes. The findings show that the algal communities in the reservoirs are relatively stable, particularly those of the filamentous cyanobacteria, chlorophytes, and prymnesiophytes with some notable exceptions, such as the abundance of diatoms, which increased in Bartlett Lake and Lake Pleasant. When in-situ data were compared with Landsat-derived reflectance data, two-band combinations were found to be the best-estimators of chlorophyll-a concentration (as a proxy for algal biomass) and total suspended sediment concentration. The ratio of the reflectance value of the red band and the blue band produced reasonable estimates for the in-situ parameters in Bartlett Lake. The ratio of the reflectance value of the green band and the blue band produced reasonable estimates for the in-situ parameters in Saguaro Lake. However, even the best performing two-band algorithm did not produce any significant correlation between reflectance and in-situ data in Lake Pleasant. Overall, remotely-sensed observations can significantly improve our understanding of the water quality as measured by algae abundance and particulate loading in Arizona Reservoirs, especially when applied over long timescales.

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Date Created
  • 2018

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Evaluating the Use of Surrogates of Marine Mammal Species Representation in Biodiversity Conservation Planning

Description

Biodiversity is required to guarantee proper ecosystem structure and function. However, increasing anthropogenic threats are causing biodiversity loss around the world at an unprecedented rate, in what has been deemed

Biodiversity is required to guarantee proper ecosystem structure and function. However, increasing anthropogenic threats are causing biodiversity loss around the world at an unprecedented rate, in what has been deemed the sixth mass extinction. To counteract this crisis, conservationists seek to improve the methods used in the design and implementation of protected areas, which help mitigate the impacts of human activities on species. Marine mammals are ecosystem engineers and important indicator species of ocean and human wellbeing. They are also disproportionally less known and more threatened than terrestrial mammals. Therefore, surrogates of biodiversity must be used to maximize their representation in conservation planning. Some of the most effective surrogates of biodiversity known have only been tested in terrestrial systems. Here I test complementarity, rarity, and environmental diversity as potential surrogates of marine mammal representation at the global scale, and compare their performance against species richness, which is the most popular surrogate used to date. I also present the first map of marine mammal complementarity, and assess its relationship with environmental variables to determine if environmental factors could also be used as surrogates. Lastly, I determine the global complementarity-based hotspots of marine mammal biodiversity, and compare their distributions against current marine protected area coverage and exposure to global indices of human threats, to elucidate the effectiveness of current conservation efforts. Results show that complementarity, rarity, and environmental diversity are all efficient surrogates, as they outcompete species richness in maximizing marine mammal species representation when solving the minimum-set coverage problem. Results also show that sea surface temperature, density, and bathymetry are the top environmental variables most associated with complementarity of marine mammals. Finally, gap analyses show that marine mammals are overall poorly protected, yet moderately exposed to hotspots of cumulative human impacts. The wide distribution of marine mammals justify global studies like the ones here presented, to determine the best strategy for their protection. Overall, my findings show that less popular surrogates of biodiversity are more effective for marine mammals and should be considered in their management, and that the expansion of protected areas in their most important habitats should be prioritized.

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Date Created
  • 2019

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Metal Organic Interactions at Hydrothermal Conditions: Useful Transformations Through Geomimicry

Description

Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to

Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to petroleum generation and to chemoautotrophic microbial communities. There have been numerous studies on the reactivity of organic compounds in water at elevated temperatures, but these studies rarely explore the consequences of inorganic solutes in hydrothermal fluids. The experiments in this thesis explore new reaction pathways of organic compounds mediated by aqueous and solid phase metals, mainly Earth-abundant copper. These experiments show that copper species have the potential to oxidize benzene and toluene, which are typically viewed as unreactive. These pathways add to the growing list of known organic transformations that are possible in natural hydrothermal systems. In addition to the characterization of reactions in natural systems, there has been recent interest in using hydrothermal conditions to facilitate organic transformations that would be useful in an applied, industrial or synthetic setting. This thesis identifies two sets of conditions that may serve as alternatives to commonplace industrial processes. The first process is the oxidation of benzene with copper to form phenol and chlorobenzene. The second is the copper mediated dehalogenation of aryl halides. Both of these processes apply the concepts of geomimicry by carrying out organic reactions under Earth-like conditions. Only water and copper are needed to implement these processes and there is no need for exotic catalysts or toxic reagents.

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Date Created
  • 2020