Matching Items (37)
Description
Molybdenum (Mo) is a key trace nutrient for biological assimilation of nitrogen, either as nitrogen gas (N2) or nitrate (NO3-). Although Mo is the most abundant metal in seawater (105 nM), its concentration is low (<5 nM) in most freshwaters today, and it was scarce in the ocean before 600 million years ago. The use of Mo for nitrogen assimilation can be understood in terms of the changing Mo availability through time; for instance, the higher Mo content of eukaryotic vs. prokaryotic nitrate reductase may have stalled proliferation of eukaryotes in low-Mo Proterozoic oceans. Field and laboratory experiments were performed to study Mo requirements for NO3- assimilation and N2 fixation, respectively. Molybdenum-nitrate addition experiments at Castle Lake, California revealed interannual and depth variability in plankton community response, perhaps resulting from differences in species composition and/or ammonium availability. Furthermore, lake sediments were elevated in Mo compared to soils and bedrock in the watershed. Box modeling suggested that the largest source of Mo to the lake was particulate matter from the watershed. Month-long laboratory experiments with heterocystous cyanobacteria (HC) showed that <1 nM Mo led to low N2 fixation rates, while 10 nM Mo was sufficient for optimal rates. At 1500 nM Mo, freshwater HC hyperaccumulated Mo intercellularly, whereas coastal HC did not. These differences in storage capacity were likely due to the presence in freshwater HC of the small molybdate-binding protein, Mop, and its absence in coastal and marine cyanobacterial species. Expression of the mop gene was regulated by Mo availability in the freshwater HC species Nostoc sp. PCC 7120. Under low Mo (<1 nM) conditions, mop gene expression was up-regulated compared to higher Mo (150 and 3000 nM) treatments, but the subunit composition of the Mop protein changed, suggesting that Mop does not bind Mo in the same manner at <1 nM Mo that it can at higher Mo concentrations. These findings support a role for Mop as a Mo storage protein in HC and suggest that freshwater HC control Mo cellular homeostasis at the post-translational level. Mop's widespread distribution in prokaryotes lends support to the theory that it may be an ancient protein inherited from low-Mo Precambrian oceans.
ContributorsGlass, Jennifer (Author) / Anbar, Ariel D (Thesis advisor) / Shock, Everett L (Committee member) / Jones, Anne K (Committee member) / Hartnett, Hilairy E (Committee member) / Elser, James J (Committee member) / Fromme, Petra (Committee member) / Arizona State University (Publisher)
Created2011
Description
Cellular redox phenomena are essential for the life of organisms. Described here is a summary of the synthesis of a number of redox-cycling therapeutic agents. The work centers on the synthesis of antitumor antibiotic bleomycin congeners. In addition, the synthesis of pyridinol analogues of alpha-tocopherol is also described. The bleomycins (BLMs) are a group of glycopeptide antibiotics that have been used clinically to treat several types of cancers. The antitumor activity of BLM is thought to be related to its degradation of DNA, and possibly RNA. Previous studies have indicated that the methylvalerate subunit of bleomycin plays an important role in facilitating DNA cleavage by bleomycin and deglycobleomycin. A series of methylvalerate analogues have been synthesized and incorporated into deglycobleomycin congeners by the use of solid-phase synthesis. All of the deglycobleomycin analogues were found to effect the relaxation of plasmid DNA. Those analogues having aromatic C4-substituents exhibited cleavage efficiency comparable to that of deglycoBLM A5. Some, but not all, of the deglycoBLM analogues were also capable of mediating sequence-selective DNA cleavage. The second project focused on the synthesis of bicyclic pyridinol analogues of alpha-tocopherol. Bicyclic pyridinol antioxidants have recently been reported to suppress the autoxidation of methyl linoleate more effectively than alpha-tocopherol. However, the complexity of the synthetic routes has hampered their further development as therapeutic agents. Described herein is a concise synthesis of two bicyclic pridinol antioxidants and a facile approach to their derivatives with simple alkyl chains attached to the antioxidant core. These analogues were shown to retain biological activity and exhibit tocopherol-like behaviour.
ContributorsCai, Xiaoqing (Author) / Hecht, Sidney M. (Thesis advisor) / Gould, Ian R (Committee member) / Hartnett, Hilairy E (Committee member) / Arizona State University (Publisher)
Created2011
Description
Black carbon (BC) is the product of incomplete combustion of biomass and fossil fuels. It is found ubiquitously in nature and is relevant to studies in atmospheric science, soil science, oceanography, and anthropology. Black carbon is best described using a combustion continuum that sub-classifies BC into slightly charred biomass, char, charcoal and soot. These sub-classifications range in particle size, formation temperature, and relative reactivity. Interest in BC has increased because of its role in the long-term storage of organic matter and the biogeochemistry of urban areas. The global BC budget is unbalanced. Production of BC greatly outweighs decomposition of BC. This suggests that there are unknown or underestimated BC removal processes, and it is likely that some of these processes are occurring in soils. However, little is known about BC reactivity in soil and especially in desert soil. This work focuses on soot BC, which is formed at higher temperatures and has a lower relative reactivity than other forms of BC. Here, I assess the contribution of soot BC to central AZ soils and use the isotopic composition of soot BC to identify sources of soot BC. Soot BC is a significant (31%) fraction of the soil organic matter in central AZ and this work suggests that desert and urban soils may be a storage reservoir for soot BC. I further identify previously unknown removal processes of soot BC found naturally in soil and demonstrate that soil soot BC undergoes abiotic (photo-oxidation) and biotic reactions. Not only is soot BC degraded by these processes, but its chemical composition is altered, suggesting that soot BC contains some chemical moieties that are more reactive than others. Because soot BC demonstrates both refractory and reactive character, it is likely that the structure of soot BC; therefore, its interactions in the environment are complex and it is not simply a recalcitrant material.
ContributorsHamilton, George (Author) / Hartnett, Hilairy E (Thesis advisor) / Herckes, Pierre (Committee member) / Hall, Sharon (Committee member) / Arizona State University (Publisher)
Created2013
Description
Human activity has increased loading of reactive nitrogen (N) in the environment, with important and often deleterious impacts on biodiversity, climate, and human health. Since the fate of N in the ecosystem is mainly controlled by microorganisms, understanding the factors that shape microbial communities becomes relevant and urgent. In arid land soils, these microbial communities and factors are not well understood. I aimed to study the role of N cycling microbes, such as the ammonia-oxidizing bacteria (AOB), the recently discovered ammonia-oxidizing archaea (AOA), and various fungal groups, in soils of arid lands. I also tested if niche differentiation among microbial populations is a driver of differential biogeochemical outcomes. I found that N cycling microbial communities in arid lands are structured by environmental factors to a stronger degree than what is generally observed in mesic systems. For example, in biological soil crusts, temperature selected for AOA in warmer deserts and for AOB in colder deserts. Land-use change also affects niche differentiation, with fungi being the major agents of N2O production in natural arid lands, whereas emissions could be attributed to bacteria in mesic urban lawns. By contrast, NO3- production in the native desert and managed soils was mainly controlled by autotrophic microbes (i.e., AOB and AOA) rather than by heterotrophic fungi. I could also determine that AOA surprisingly responded positively to inorganic N availability in both short (one month) and long-term (seven years) experimental manipulations in an arid land soil, while environmental N enrichment in other ecosystem types is known to favor AOB over AOA. This work improves our predictions of ecosystem response to anthropogenic N increase and shows that paradigms derived from mesic systems are not always applicable to arid lands. My dissertation also highlights the unique ecology of ammonia oxidizers and draws attention to the importance of N cycling in desert soils.
ContributorsMarusenko, Yevgeniy (Author) / Hall, Sharon J (Thesis advisor) / Garcia-Pichel, Ferran (Thesis advisor) / Mclain, Jean E (Committee member) / Schwartz, Egbert (Committee member) / Arizona State University (Publisher)
Created2013
Description
Irrigation agriculture has been heralded as the solution to feeding the world's growing population. To this end, irrigation agriculture is both extensifying and intensifying in arid regions across the world in an effort to create highly productive agricultural systems. Over one third of modern irrigated fields, however, show signs of serious soil degradation, including salinization and waterlogging, which threaten the productivity of these fields and the world's food supply. Surprisingly, little ecological data on agricultural soils have been collected to understand and address these problems. How, then, can expanding and intensifying modern irrigation systems remain agriculturally productive for the long-term? Archaeological case studies can provide critical insight into how irrigated agricultural systems may be sustainable for hundreds, if not thousands, of years. Irrigation systems in Mesopotamia, for example, have been cited consistently as a cautionary tale of the relationship between mismanaged irrigation systems and the collapse of civilizations, but little data expressly link how and why irrigation failed in the past. This dissertation presents much needed ecological data from two different regions of the world - the Phoenix Basin in southern Arizona and the Pampa de Chaparrí on the north coast of Peru - to explore how agricultural soils were affected by long-term irrigation in a variety of social and economic contexts, including the longevity and intensification of irrigation agriculture. Data from soils in prehispanic and historic agricultural fields indicate that despite long-lived and intensive irrigation farming, farmers in both regions created strategies to sustain large populations with irrigation agriculture for hundreds of years. In the Phoenix Basin, Hohokam and O'odham farmers relied on sedimentation from irrigation water to add necessary fine sediments and nutrients to otherwise poor desert soils. Similarly, on the Pampa, farmers relied on sedimentation in localized contexts, but also constructed fields with ridges and furrows to draw detrimental salts away from planting surfaces in the furrows on onto the ridges. These case studies are then compared to failing modern and ancient irrigated systems across the world to understand how the centralization of management may affect the long-term sustainability of irrigation agriculture.
ContributorsStrawhacker, Colleen (Author) / Spielmann, Katherine A. (Thesis advisor) / Hall, Sharon J (Committee member) / Nelson, Margaret C. (Committee member) / Sandor, Jonathan A (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation examines two topics of emerging interest in the field of organic geochemistry. The topic of the first portion of the dissertation is cold organic geochemistry on Saturn's moon Titan. Titan has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most famously as lakes. Photochemical reactions produce solid organics in Titan's atmosphere, and these materials settle onto the surface. At the surface, liquids can interact with solids, and geochemical processes can occur. To better understand these processes, I developed a thermodynamic model that can be used to calculate the solubilities of gases and solids in liquid hydrocarbons at cryogenic temperatures. The model was parameterized using experimental data, and provides a good fit to the data. Application of the model to Titan reveals that the equilibrium composition of surface liquids depends on the abundance of methane in the local atmosphere. The model also indicates that solid acetylene should be quite soluble in surface liquids, which implies that acetylene-rich rocks should be susceptible to chemical erosion, and acetylene evaporites may form on Titan. In the latter half of this dissertation, I focus on hot organic geochemistry below the surface of the Earth. Organic compounds are common in sediments. Burial of sediments leads to changes in physical and chemical conditions, promoting organic reactions. An important organic reaction in subsurface environments is decarboxylation, which generates hydrocarbons and carbon dioxide from simple organic acids. Fundamental knowledge about decarboxylation is required to better understand how the organic and inorganic compositions of sediments evolve in response to changing geochemical conditions. I performed experiments with the model compound phenylacetic acid to obtain information about mechanisms of decarboxylation in hydrothermal fluids. Patterns in rates of decarboxylation of substituted phenylacetic acids point to a mechanism that proceeds through a ring-protonated zwitterion of phenylacetic acid. In contrast, substituted sodium phenylacetates exhibit a different kinetic pattern, one that is consistent with the formation of the benzyl anion as an intermediate. Results from experiments with added hydrochloric acid or sodium hydroxide, and deuterated water agree with these interpretations. Thus, speciation dictates mechanism of decarboxylation.
ContributorsGlein, Christopher R (Author) / Shock, Everett L (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Zolotov, Mikhail Y (Committee member) / Williams, Lynda B (Committee member) / Gould, Ian R (Committee member) / Arizona State University (Publisher)
Created2012
Description
The global transport and deposition of anthropogenic nitrogen (N) to downwind ecosystems are significant and continue to increase. Indeed, atmospheric deposition can be a significant source of N to many watersheds, including those in remote, unpopulated areas. Bacterial denitrification in lake sediments may ameliorate the effects of N loading by converting nitrate (NO3-) to N2 gas. Denitrification also produces nitrous oxide (N2O), a potent greenhouse gas. The ecological effects of atmospheric N inputs in terrestrial ecosystems and the pelagic zone of lakes have been well documented; however, similar research in lake sediments is lacking. This project investigates the effects N of deposition on denitrification and N2O production in lakes. Atmospheric N inputs might alter the availability of NO3- and other key resources to denitrifiers. Such altered resources could influence denitrification, N2O production, and the abundance of denitrifying bacteria in sediments. The research contrasts these responses in lakes at the ends of gradients of N deposition in Colorado and Norway. Rates of denitrification and N2O production were elevated in the sediments of lakes subject to anthropogenic N inputs. There was no evidence, however, that N deposition has altered sediment resources or the abundance of denitrifiers. Further investigation into the dynamics of nitric oxide, N2O, and N2 during denitrification found no difference between deposition regions. Regardless of atmospheric N inputs, sediments from lakes in both Norway and Colorado possess considerable capacity to remove NO3- by denitrification. Catchment-specific properties may influence the denitrifying community more strongly than the rate of atmospheric N loading. In this regard, sediments appear to be insulated from the effects of N deposition compared to the water column. Lastly, surface water N2O concentrations were greater in high-deposition lakes compared to low-deposition lakes. To understand the potential magnitude of deposition-induced N2O production, the greenhouse gas inventory methodology of Intergovernmental Panel on Climate Change was applied to available datasets. Estimated emissions from lakes are 7-371 Gg N y-1, suggesting that lakes could be an important source of N2O.
ContributorsMcCrackin, Michelle Lynn (Author) / Elser, James J (Thesis advisor) / Grimm, Nancy (Committee member) / Hall, Sharon J (Committee member) / Hartnett, Hilairy E (Committee member) / Souza, Valeria (Committee member) / Arizona State University (Publisher)
Created2010
Description
This thesis explores the independent effects of the manipulation of rocks into alignments, prehistoric farming, and season on soil properties in two areas with a history of prehistoric agriculture in central Arizona, Pueblo la Plata within the Agua Fria National Monument (AFNM), and an archaeological site north of the Phoenix basin along Cave Creek (CC). Soil properties, annual herbaceous biomass and the physical properties of alignments and surface soils were measured and compared across the landscape, specifically on: 1) agricultural rock alignments that were near the archaeological site 2) geologically formed rock alignments that were located 0.5-1 km away from settlements; and 3) areas both near and far from settlements where rock alignments were absent. At AFNM, relatively well-built rock alignments have altered soil properties and processes while less-intact alignments at CC have left few legacies.
ContributorsTrujillo, Jolene Eve (Author) / Hall, Sharon J (Thesis advisor) / Collins, Scott L. (Committee member) / Spielmann, Katherine A. (Committee member) / Arizona State University (Publisher)
Created2011
Description
More than half of all accessible freshwater has been appropriated for human use, and a substantial portion of terrestrial ecosystems have been transformed by human action. These impacts are heaviest in urban ecosystems, where impervious surfaces increase runoff, water delivery and stormflows are managed heavily, and there are substantial anthropogenic sources of nitrogen (N). Urbanization also frequently results in creation of intentional novel ecosystems. These "designed" ecosystems are fashioned to fulfill particular needs of the residents, or ecosystem services. In the Phoenix, Arizona area, the augmentation and redistribution of water has resulted in numerous component ecosystems that are atypical for a desert environment. Because these systems combine N loading with the presence of water, they may be hot spots of biogeochemical activity. The research presented here illustrates the types of hydrological modifications typical of desert cities and documents the extent and distribution of common designed aquatic ecosystems in the Phoenix metropolitan area: artificial lakes and stormwater retention basins. While both ecosystems were designed for other purposes (recreation/aesthetics and flood abatement, respectively), they have the potential to provide the added ecosystem service of N removal via denitrification. However, denitrification in urban lakes is likely to be limited by the rate of diffusion of nitrate into the sediment. Retention basins export some nitrate to groundwater, but grassy basins have higher denitrification rates than xeriscaped ones, due to higher soil moisture and organic matter content. An economic valuation of environmental amenities demonstrates the importance of abundant vegetation, proximity to water, and lower summer temperatures throughout the region. These amenities all may be provided by designed, water-intensive ecosystems. Some ecosystems are specifically designed for multiple uses, but maximizing one ecosystem service often entails trade-offs with other services. Further investigation into the distribution, bundling, and tradeoffs among water-related ecosystem services shows that some types of services are constrained by the hydrogeomorphology of the area, while for others human engineering and the creation of designed ecosystems has enabled the delivery of hydrologic ecosystem services independent of natural constraints.
ContributorsLarson, Elisabeth Knight (Author) / Grimm, Nancy (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Fisher, Stuart G. (Committee member) / Anderies, John M (Committee member) / Lohse, Kathleen A (Committee member) / Arizona State University (Publisher)
Created2010
Description
As an industrial society, humans have increasingly separated agricultural processes from natural ecosystems. Many areas of the Southwestern US, however, maintain traditional practices that link agricultural systems to the natural environment. One such practice, diverting river water into fields via earthen irrigation canals, allows ditch water to recharge groundwater and riparian vegetation to prosper along canal banks. As there is growing interest in managing landscapes for multiple ecosystem services, this study was undertaken to determine if irrigation canals function as an extension of the riparian corridor. I was specifically interested in determining if the processes within semi-arid streams that drive riparian plant community structure are manifested in earthen irrigation ditches. I examined herbaceous and woody vegetation along the middle Verde River, AZ, USA and three adjacent irrigation ditches across six months. I also collected sieved hydrochores--seeds dispersing through water--within ditches and the river twelve times. Results indicate that ditch vegetation was similar to streamside river vegetation in abundance (cover and basal area) due to surface water availability but more diverse than river streamside vegetation due to high heterogeneity. Compositionally, herbaceous vegetation along the ditch was most similar to the river banks, while low disturbance fostered woody vegetation along the ditches similar to high floodplain and river terrace vegetation. Hydrochore richness and abundance within the river was dependent on seasonality and stream discharge, but these relationships were dampened in the ditches. Species-specific strategies of hydrochory, however, did emerge in both systems. Strategies include pulse species, which disperse via hydrochory in strict accordance with their restricted dispersal windows, constant species, which are year round hydrochores, and combination species, which show characteristics of both. There was high overlap in the composition of hydrochores in the two systems, with obligate wetland species abundant in both. Upland species were more seasonally constant and abundant in the ditch water than the river. The consistency of river processes and similarity of vegetation suggest that earthen irrigation ditches do function as an extension of the riparian corridor. Thus, these man-made irrigation ditches should be considered by stakeholders for their multiple ecosystem services.
ContributorsBetsch, Jacqueline Michelle (Author) / Stromberg, Juliet C. (Thesis advisor) / Hall, Sharon J (Committee member) / Merritt, David M. (Committee member) / Arizona State University (Publisher)
Created2010