Matching Items (44)
Filtering by
- Resource Type: Text
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
The focus of this thesis is to study dissolved organic carbon composition and reactivity along the Colorado and Green Rivers. Dissolved organic carbon (DOC) in large-scale, managed rivers is relatively poorly studied as most literature has focused on pristine unmanaged rivers. The Colorado River System is the 7th largest in the North America; there are seventeen large dams along the Colorado and Green River. DOC in rivers and in the lakes formed by dams (reservoirs) undergo photo-chemical and bio-degradation. DOC concentration and composition in these systems were investigated using bulk concentration, optical properties, and fluorescence spectroscopy. The riverine DOC concentration decreased from upstream to downstream but there was no change in the specific ultraviolet absorbance at 254 nm (SUVA254). Total fluorescence also decreased along the river. In general, the fluorescence index (FI) increased slightly, the humification index (HIX) decreased, and the freshness index (β/α) increased from upstream to downstream. Photo-oxidation and biodegradation experiments were used to determine if the observed changes in DOC composition along the river could be driven by these biogeochemical alteration processes.
In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study.
The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation.
In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study.
The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation.
ContributorsBowman, Margaret (Author) / Hartnett, Hilairy E (Thesis advisor) / Hayes, Mark A. (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2015
Description
Climate change will result not only in changes in the mean state of climate but also on changes in variability. However, most studies of the impact of climate change on ecosystems have focused on the effect of changes in the central tendency. The broadest objective of this thesis was to assess the effects of increased interannual precipitation variation on ecosystem functioning in grasslands. In order to address this objective, I used a combination of field experimentation and data synthesis. Precipitation manipulations on the field experiments were carried out using an automated rainfall manipulation system developed as part of this dissertation. Aboveground net primary production responses were monitored during five years. Increased precipitation coefficient of variation decreased primary production regardless of the effect of precipitation amount. Perennial-grass productivity significantly decreased while shrub productivity increased as a result of enhanced precipitation variance. Most interesting is that the effect of precipitation variability increased through time highlighting the existence of temporal lags in ecosystem response.
Further, I investigated the effect of precipitation variation on functional diversity on the same experiment and found a positive response of diversity to increased interannual precipitation variance. Functional evenness showed a similar response resulting from large changes in plant-functional type relative abundance including decreased grass and increased shrub cover while functional richness showed non-significant response. Increased functional diversity ameliorated the direct negative effects of precipitation variation on ecosystem ANPP but did not control ecosystem stability where indirect effects through the dominant plant-functional type determined ecosystem stability.
Analyses of 80 long-term data sets, where I aggregated annual productivity and precipitation data into five-year temporal windows, showed that precipitation variance had a significant effect on aboveground net primary production that is modulated by mean precipitation. Productivity increased with precipitation variation at sites where mean annual precipitation is less than 339 mm but decreased at sites where precipitation is higher than 339 mm. Mechanisms proposed to explain patterns include: differential ANPP response to precipitation among sites, contrasting legacy effects and soil water distribution.
Finally, increased precipitation variance may impact global grasslands affecting plant-functional types in different ways that may lead to state changes, increased erosion and decreased stability that can in turn limit the services provided by these valuable ecosystems.
Further, I investigated the effect of precipitation variation on functional diversity on the same experiment and found a positive response of diversity to increased interannual precipitation variance. Functional evenness showed a similar response resulting from large changes in plant-functional type relative abundance including decreased grass and increased shrub cover while functional richness showed non-significant response. Increased functional diversity ameliorated the direct negative effects of precipitation variation on ecosystem ANPP but did not control ecosystem stability where indirect effects through the dominant plant-functional type determined ecosystem stability.
Analyses of 80 long-term data sets, where I aggregated annual productivity and precipitation data into five-year temporal windows, showed that precipitation variance had a significant effect on aboveground net primary production that is modulated by mean precipitation. Productivity increased with precipitation variation at sites where mean annual precipitation is less than 339 mm but decreased at sites where precipitation is higher than 339 mm. Mechanisms proposed to explain patterns include: differential ANPP response to precipitation among sites, contrasting legacy effects and soil water distribution.
Finally, increased precipitation variance may impact global grasslands affecting plant-functional types in different ways that may lead to state changes, increased erosion and decreased stability that can in turn limit the services provided by these valuable ecosystems.
ContributorsGherardi Arbizu, Laureano (Author) / Sala, Osvaldo E. (Thesis advisor) / Childers, Daniel (Committee member) / Grimm, Nancy (Committee member) / Hall, Sharon (Committee member) / Wu, Jingle (Committee member) / Arizona State University (Publisher)
Created2014
Description
Coal bed natural gas (CBNG) production has become a significant contribution to the nation's energy supply. Large volumes of water are generated as a byproduct of CBNG extraction, of which this "product water" is relatively high in sodium. High sodicity reduces water quality and limits environmentally compliant disposal options for producers. Crop irrigation with CBNG product water complies with state and federal laws and is a disposal method that also provides a beneficial use to private landowners. However, this disposal method typically requires gypsum and sulfur soil amendments due to the high levels of sodium in the water, which can reduce soil infiltration and hydraulic conductivity. In this study, I tested a new product called Salt Extractor that was marketed to CBNG producers to ameliorate the negative effects of high sodicity. The experiment was conducted in the Powder River Basin of Wyoming. I used a random block design to compare the soil and vegetation properties of plots following application with CBNG product water and treatments of either Salt Extractor, gypsum and sulfur (conventional), or no treatment (control). Data was analyzed by comparing the amount of change between treatments after watering. Results demonstrated the known ability of gypsum and sulfur to lower the relative sodicity of the soil. Plots treated with Salt Extractor, however, did not improve relative levels of sodicity and exhibited no favorable benefits to vegetation.
ContributorsAdams, Shelly (Author) / Hall, Sharon (Thesis advisor) / Chew, Matt (Committee member) / Stromberg, Juliet (Committee member) / Arizona State University (Publisher)
Created2011
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
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
In many natural systems aqueous geochemical conditions dictate the reaction pathways of organic compounds. Geologic settings that span wide ranges in temperature, pressure, and composition vastly alter relative reaction rates and resulting organic abundances. The dependence of organic reactions on these variables contributes to planetary-scale nutrient cycling, and suggests that relative abundances of organic compounds can reveal information about inaccessible geologic environments, whether from the terrestrial subsurface, remote planetary settings, or even the distant past (if organic abundances are well preserved). Despite their relevance to planetary modeling and exploration, organic reactions remain poorly characterized under geochemically relevant conditions, especially in terms of their reaction kinetics, mechanisms, and equilibria.
In order to better understand organic transformations in natural systems, the reactivities of oxygen- and nitrogen-bearing organic functional groups were investigated under experimental hydrothermal conditions, at 250°C and 40 bar. The model compounds benzylamine and α-methylbenzylamine were used as analogs to environmentally relevant amines, ultimately elucidating two dominant deamination mechanisms for benzylamine, SN1 and SN2, and a single SN1 mechanism for deamination of α-methylbenzylamine. The presence of unimolecular and bimolecular mechanisms has implications for temperature dependent kinetics, indicating that Arrhenius rate extrapolation is currently unreliable for deamination.
Hydrothermal experiments with benzyl alcohol, benzylamine, dibenzylamine, or tribenzylamine as the starting material indicate that substitution reactions between these compounds (and others) are reversible and approach metastable equilibrium after 72 hours. These findings suggest that relative ratios of organic compounds capable of substitution reactions could be targeted as tracers of inaccessible geochemical conditions.
Metastable equilibria for organic reactions were investigated in a natural low-temperature serpentinizing continental system. Serpentinization is a water-rock reaction which generates hyperalkaline, reducing conditions. Thermodynamic calculations were performed for reactions between dissolved inorganic carbon and hydrogen to produce methane, formate, and acetate. Quantifying conditions that satisfy equilibrium for these reactions allows subsurface conditions to be predicted. These calculations also lead to hypotheses regarding active microbial processes during serpentinization.
In order to better understand organic transformations in natural systems, the reactivities of oxygen- and nitrogen-bearing organic functional groups were investigated under experimental hydrothermal conditions, at 250°C and 40 bar. The model compounds benzylamine and α-methylbenzylamine were used as analogs to environmentally relevant amines, ultimately elucidating two dominant deamination mechanisms for benzylamine, SN1 and SN2, and a single SN1 mechanism for deamination of α-methylbenzylamine. The presence of unimolecular and bimolecular mechanisms has implications for temperature dependent kinetics, indicating that Arrhenius rate extrapolation is currently unreliable for deamination.
Hydrothermal experiments with benzyl alcohol, benzylamine, dibenzylamine, or tribenzylamine as the starting material indicate that substitution reactions between these compounds (and others) are reversible and approach metastable equilibrium after 72 hours. These findings suggest that relative ratios of organic compounds capable of substitution reactions could be targeted as tracers of inaccessible geochemical conditions.
Metastable equilibria for organic reactions were investigated in a natural low-temperature serpentinizing continental system. Serpentinization is a water-rock reaction which generates hyperalkaline, reducing conditions. Thermodynamic calculations were performed for reactions between dissolved inorganic carbon and hydrogen to produce methane, formate, and acetate. Quantifying conditions that satisfy equilibrium for these reactions allows subsurface conditions to be predicted. These calculations also lead to hypotheses regarding active microbial processes during serpentinization.
ContributorsRobinson, Kirtland J (Author) / Shock, Everett L (Thesis advisor) / Herckes, Pierre (Committee member) / Hartnett, Hilairy E (Committee member) / Anbar, Ariel D (Committee member) / Arizona State University (Publisher)
Created2017
Description
Water is a critical resource for future human missions, and is necessary for understanding the evolution of the Solar System. The Moon and Mars have water in various forms and are therefore high-priority targets in the search for accessible extraterrestrial water. Complementary remote sensing analyses coupled with laboratory and field studies are necessary to provide a scientific context for future lunar and Mars exploration. In this thesis, I use multiple techniques to investigate the presence of water-ice at the lunar poles and the properties of martian chloride minerals, whose evolution is intricately linked with liquid water.
Permanently shadowed regions (PSRs) at the lunar poles may contain substantial water ice, but radar signatures at PSRs could indicate water ice or large block populations. Mini-RF radar and Lunar Reconnaissance Orbiter Camera Narrow Angle Camera (LROC NAC) products were used to assess block abundances where radar signatures indicated potential ice deposits. While the majority of PSRs in this study indicated large block populations and a low likelihood of water ice, one crater – Rozhdestvenskiy N – showed indirect indications of water ice in its interior.
Chloride deposits indicate regions where the last substantial liquid water existed on Mars. Major ion abundances and expected precipitation sequences of terrestrial chloride brines could provide context for assessing the provenance of martian chloride deposits. Chloride minerals are most readily distinguished in the far-infrared (45+ μm), where their fundamental absorption features are strongest. Multiple chloride compositions and textures were characterized in far-infrared emission for the first time. Systematic variations in the spectra were observed; these variations will allow chloride mineralogy to be determined and large variations in texture to be constrained.
In the present day, recurring slope lineae (RSL) may indicate water flow, but fresh water is not stable on Mars. However, dissolved chloride could allow liquid water to flow transiently. Using Thermal Emission Imaging System (THEMIS) data, I determined that RSL are most likely not fed by chloride-rich brines on Mars. Substantial amounts of salt would be consumed to produce a surface water flow; therefore, these features are therefore thought to instead be surface darkening due to capillary wicking.
Permanently shadowed regions (PSRs) at the lunar poles may contain substantial water ice, but radar signatures at PSRs could indicate water ice or large block populations. Mini-RF radar and Lunar Reconnaissance Orbiter Camera Narrow Angle Camera (LROC NAC) products were used to assess block abundances where radar signatures indicated potential ice deposits. While the majority of PSRs in this study indicated large block populations and a low likelihood of water ice, one crater – Rozhdestvenskiy N – showed indirect indications of water ice in its interior.
Chloride deposits indicate regions where the last substantial liquid water existed on Mars. Major ion abundances and expected precipitation sequences of terrestrial chloride brines could provide context for assessing the provenance of martian chloride deposits. Chloride minerals are most readily distinguished in the far-infrared (45+ μm), where their fundamental absorption features are strongest. Multiple chloride compositions and textures were characterized in far-infrared emission for the first time. Systematic variations in the spectra were observed; these variations will allow chloride mineralogy to be determined and large variations in texture to be constrained.
In the present day, recurring slope lineae (RSL) may indicate water flow, but fresh water is not stable on Mars. However, dissolved chloride could allow liquid water to flow transiently. Using Thermal Emission Imaging System (THEMIS) data, I determined that RSL are most likely not fed by chloride-rich brines on Mars. Substantial amounts of salt would be consumed to produce a surface water flow; therefore, these features are therefore thought to instead be surface darkening due to capillary wicking.
ContributorsMitchell, Julie (Author) / Christensen, Philip R. (Thesis advisor) / Bell Iii, James F (Committee member) / Desch, Steven J (Committee member) / Hartnett, Hilairy E (Committee member) / Robinson, Mark S (Committee member) / Arizona State University (Publisher)
Created2017
Description
Aboveground net primary production (ANPP) and belowground net primary production (BNPP) may not be influenced equally by the same factors in arid grasslands. Precipitation is known to affect ANPP and BNPP, while soil fauna such as nematodes affect the BNPP through herbivory and predation. This study on black grama grass (Bouteloua eriopoda) in the Chihuahuan Desert investigates the effects of precipitation and nematode presence or absence on net primary production (NPP) as well as the partitioning between the aboveground and belowground components, in this case, the fraction of total net primary production occurring belowground (fBNPP). I used a factorial experiment to investigate the effects of both precipitation and nematode presence on the components of NPP. I used rainout shelters and an irrigation system to alter precipitation totals, while I used defaunated and re-inoculated soil for the nematode treatments. Precipitation treatment and seasonal soil moisture had no effect on the BNPP and a nonsignificant positive effect on the ANPP. The fBNPP decreased with increasing precipitation and seasonal soil moisture, though without a significant effect. No predator nematodes were found in any of the microcosms at the end of the experiment, though other functional groups of nematodes, including herbivores, were found in the microcosms. Total nematode numbers did not vary significantly between nematode treatments, indicating that the inoculation process did not last for the whole experiment or that nematodes had little plant material to eat and resulted in low population density. Nematode presence did not affect the BNPP, ANPP, or the fBNPP. There were no significant interactions between precipitation and nematode treatment. The results are inconclusive, possibly as a result of ecosystem trends during an unusually high precipitation year, as well as the very low NPP values in the experiment that correlated with low nematode community numbers.
ContributorsWiedenfeld, Amy (Author) / Sala, Osvaldo (Thesis advisor) / Gerber, Leah (Committee member) / Hall, Sharon (Committee member) / Arizona State University (Publisher)
Created2018