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Description
The present understanding of the formation and evolution of the earliest bodies in the Solar System is based in large part on geochemical and isotopic evidences contained within meteorites. The differentiated meteorites (meteorites originating from bodies that have experienced partial to complete melting) are particularly useful for deciphering magmatic processes

The present understanding of the formation and evolution of the earliest bodies in the Solar System is based in large part on geochemical and isotopic evidences contained within meteorites. The differentiated meteorites (meteorites originating from bodies that have experienced partial to complete melting) are particularly useful for deciphering magmatic processes occurring in the early Solar System. A rare group of differentiated meteorites, the angrites, are uniquely suited for such work. The angrites have ancient crystallization ages, lack secondary processing, and have been minimally affected by shock metamorphism, thus allowing them to retain their initial geochemical and isotopic characteristics at the time of formation. The scarcity of angrite samples made it difficult to conduct comprehensive investigations into the formation history of this unique meteorite group. However, a dramatic increase in the number of angrites recovered in recent years presents the opportunity to expand our understanding of their petrogenesis, as well as further refine our knowledge of the initial isotopic abundances in the early Solar System as recorded by their isotopic systematics. Using a combination of geochemical tools (radiogenic isotope chronometers and trace element chemistry), I have investigated the petrogenetic history of a group of four angrites that sample a range of formation conditions (cooling histories) and crystallization ages. Through isotope ratio measurements, I have examined a comprehensive set of long- and short-lived radiogenic isotope systems (26Al-26Mg, 87Rb-87Sr, 146Sm-142Nd, 147Sm-143Nd, and 176Lu-176Hf) within these four angrites. The results of these measurements provide information regarding crystallization ages, as well as revised estimates for the initial isotopic abundances of several key elements in the early Solar System. The determination of trace element concentrations in individual mineral phases, as well as bulk rock samples, provides important constraints on magmatic processes occurring on the angrite parent body. The measured trace element abundances are used to estimate the composition of the parent melts of individual angrites, examine crystallization conditions, and investigate possible geochemical affinities between various angrites. The new geochemical and isotopic measurements presented here significantly expand our understanding of the geochemical conditions found on the angrite parent body and the environment in which these meteorites formed.
ContributorsSanborn, Matthew E (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Sharp, Thomas (Committee member) / Clarke, Amanda (Committee member) / Williams, Lynda (Committee member) / Carlson, Richard (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The presence of a number of extinct radionuclides in the early Solar System (SS) is known from geochemical and isotopic studies of meteorites and their components. The half-lives of these isotopes are short relative to the age of the SS, such that they have now decayed to undetectable levels. They

The presence of a number of extinct radionuclides in the early Solar System (SS) is known from geochemical and isotopic studies of meteorites and their components. The half-lives of these isotopes are short relative to the age of the SS, such that they have now decayed to undetectable levels. They can be inferred to exist in the early SS from the presence of their daughter nuclides in meteoritic materials that formed while they were still extant. The extinct radionuclides are particularly useful as fine-scale chronometers for events in the early SS. They can also be used to help constrain the astrophysical setting of the formation of the SS because their short half-lives and unique formation environments yield information about the sources and timing of delivery of material to the protoplanetary disk. Some extinct radionuclides are considered evidence that the Sun interacted with a massive star (supernova) early in its history. The abundance of 60Fe in the early SS is particularly useful for constraining the astrophysical environment of the Sun's formation because, if present in sufficient abundance, its only likely source is injection from a nearby supernova. The initial SS abundance of 60Fe is poorly constrained at the present time, with estimates varying by 1-2 orders of magnitude. I have determined the 60Fe-60Ni isotope systematics of ancient, well-preserved meteorites using high-precision mass spectrometry to better constrain the initial SS abundance of 60Fe. I find identical estimates of the initial 60Fe abundance from both differentiated basaltic meteorites and from components of primitive chondrites formed in the Solar nebula, which suggest a lower 60Fe abundance than other recent estimates. With recent improved meteorite collection efforts there are more rare ungrouped meteorites being found that hold interesting clues to the origin and evolution of early SS objects. I use the 26Al-26Mg extinct radionuclide chronometer to constrain the ages of several recently recovered meteorites that sample previously unknown asteroid lithologies, including the only know felsic meteorite from an asteroid and two other ungrouped basaltic achondrites. These results help broaden our understanding of the timescales involved in igneous differentiation processes in the early SS.
ContributorsSpivak-Birndorf, Lev (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Timmes, Francis (Committee member) / Williams, Lynda (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Harsh environments have conditions that make collecting scientific data difficult with existing commercial-off-the-shelf technology. Micro Electro Mechanical Systems (MEMS) technology is ideally suited for harsh environment characterization and operation due to the wide range of materials available and an incredible array of different sensing techniques while providing small device size,

Harsh environments have conditions that make collecting scientific data difficult with existing commercial-off-the-shelf technology. Micro Electro Mechanical Systems (MEMS) technology is ideally suited for harsh environment characterization and operation due to the wide range of materials available and an incredible array of different sensing techniques while providing small device size, low power consumption, and robustness. There were two main objectives of the research conducted. The first objective was to design, fabricate, and test novel sensors that measure the amount of exposure to ionizing radiation for a wide range of applications including characterization of harsh environments. Two types of MEMS ionizing radiation dosimeters were developed. The first sensor was a passive radiation-sensitive capacitor-antenna design. The antenna's emitted frequency of peak-intensity changed as exposure time to radiation increased. The second sensor was a film bulk acoustic-wave resonator, whose resonant frequency decreased with increasing ionizing radiation exposure time. The second objective was to develop MEMS sensor systems that could be deployed to gather scientific data and to use that data to address the following research question: do temperature and/or conductivity predict the appearance of photosynthetic organisms in hot springs. To this end, temperature and electrical conductivity sensor arrays were designed and fabricated based on mature MEMS technology. Electronic circuits and the software interface to the electronics were developed for field data collection. The sensor arrays utilized in the hot springs yielded results that support the hypothesis that temperature plays a key role in determining where the photosynthetic organisms occur. Additionally, a cold-film fluidic flow sensor was developed, which is suitable for near-boiling temperature measurement. Future research should focus on (1) developing a MEMS pH sensor array with integrated temperature, conductivity, and flow sensors to provide multi-dimensional data for scientific study and (2) finding solutions to biofouling and self-calibration, which affects sensor performance over long-term deployment.
ContributorsOiler, Jonathon (Author) / Yu, Hongyu (Thesis advisor) / Anbar, Ariel (Committee member) / Hartnett, Hilairy (Committee member) / Scannapieco, Evan (Committee member) / Timmes, Francis (Committee member) / Arizona State University (Publisher)
Created2013
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Description
ABSTRACT Enzyme-Induced Carbonate Precipitation (EICP) using a plant-derived form of the urease enzyme to induce the precipitation of calcium carbonate (CaCO3) shows promise as a method of stabilizing soil for the mitigation of fugitive dust. Fugitive dust is a significant problem in Arizona, particularly in Maricopa County. Maricopa County is

ABSTRACT Enzyme-Induced Carbonate Precipitation (EICP) using a plant-derived form of the urease enzyme to induce the precipitation of calcium carbonate (CaCO3) shows promise as a method of stabilizing soil for the mitigation of fugitive dust. Fugitive dust is a significant problem in Arizona, particularly in Maricopa County. Maricopa County is an EPA air quality non-attainment zone, due primarily to fugitive dust, which presents a significant health risk to local residents. Conventional methods for fugitive dust control, including the application of water, are either ineffective in arid climates, very expensive, or limited to short term stabilization. Due to these limitations, engineers are searching for new and more effective ways to stabilize the soil and reduce wind erosion. EICP employs urea hydrolysis, a process in which carbonate precipitation is catalyzed by the urease enzyme, a widely occurring protein found in many plants and microorganisms. Wind tunnel experiments were conducted in the ASU/NASA Planetary Wind Tunnel to evaluate the use of EICP as a means to stabilize soil against fugitive dust emission. Three different soils were tested, including a native Arizona silty-sand, a uniform fine to medium grained silica sand, and mine tailings from a mine in southern Arizona. The test soil was loosely placed in specimen container and the surface was sprayed with an aqueous solution containing urea, calcium chloride, and urease enzyme. After a short period of time to allow for CaCO3 precipitation, the specimens were tested in the wind tunnel. The completed tests show that EICP can increase the detachment velocity compared to bare or wetted soil and thus holds promise as a means of mitigating fugitive dust emissions.
ContributorsKnorr, Brian (Author) / Kavazanjian, Edward (Thesis advisor) / Houston, Sandra (Committee member) / Zapata, Claudia (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The origin of the solar system and formation of planets such as Earth are among the most fascinating, outstanding scientific problems. From theoretical models to natural observations, it is possible to infer a general way of how the solar system evolved from the gravitational collapse of the molecular cloud to

The origin of the solar system and formation of planets such as Earth are among the most fascinating, outstanding scientific problems. From theoretical models to natural observations, it is possible to infer a general way of how the solar system evolved from the gravitational collapse of the molecular cloud to accretion and differentiation of planetary-sized bodies. This dissertation attempts to place additional constraints on the source, distribution, and evolution of chemical variability in the early solar system, Mars, and Earth.

A new method was developed for the measurement of titanium isotopes in calcium-aluminum-rich inclusions (CAIs) by laser ablation multi-collector inductively coupled plasma mass spectrometry. The isotopic compositions of 17 Allende CAIs define a narrow range with clearly resolved excesses in 46Ti and 50Ti and suggests that "normal" CAIs formed from a relatively uniform reservoir. Petrologic and isotopic analysis of a new FUN (Fractionated and Unknown Nuclear effects) CAI suggests that normal and FUN CAIs condensed in similar environments, but subsequently evolved under vastly different conditions.

Volatiles may have influenced the formation and evolution of basaltic magmas on Mars. Light lithophile element (LLE) and fluorine (F) concentrations and isotopic compositions of pyroxene determined in situ in several Martian meteorites suggests that the primary magmatic signature of LLE and F zonation in Shergottite pyroxene has been disturbed by post-crystallization diffusive equilibration. Using relevant crystal-melt partition coefficients the F contents for Martian meteorite parental melts are ~910 and ~220 ppm. Estimates of the F content in the Shergottite and Nakhlite source regions are similar to that of mid-ocean ridge basalts (MORB) and ocean island basalts (OIB), respectively, here on Earth.

Noble gas systematics of OIBs relative to MORBs, suggests OIBs preferentially sample a primordial reservoir located within Earth's mantle. Geodynamic calculations were performed to investigate the time-dependent rate of material entrained into plumes from these primordial reservoirs. These models predict melts rising to the surface will contain variable proportions of primordial material. The results demonstrate that although high 3He/4He ratios may mandate a mantle plume that samples a primordial reservoir, more MORB-like 3He/4He ratios in OIBs do not preclude a deep plume source.
ContributorsWilliams, Curtis Davis (Author) / Wadhwa, Meenakshi (Thesis advisor) / McNamara, Allen K (Committee member) / Bell, David R. (Committee member) / Garnero, Edward J (Committee member) / Young, Patrick (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Boron concentrations and isotopic composition of phlogopite mica, amphibole, and selected coexisting anhydrous phases in mantle-derived xenoliths from the Kaapvaal Craton were measured by secondary ion mass spectrometry in an effort to better understand the B isotope geochemistry of the subcontinental lithospheric mantle (SCLM) and its implications for the global

Boron concentrations and isotopic composition of phlogopite mica, amphibole, and selected coexisting anhydrous phases in mantle-derived xenoliths from the Kaapvaal Craton were measured by secondary ion mass spectrometry in an effort to better understand the B isotope geochemistry of the subcontinental lithospheric mantle (SCLM) and its implications for the global geochemical cycle of B in the mantle. These samples display a wide, and previously unrecognized, range in their boron contents and isotopic compositions reflecting a complex history involving melt depletion and metasomatism by subduction- and plume-derived components, as well as late stage isotopic exchange related to kimberlite emplacements. Micas from ancient lithospheric harzburgite metasomatized by slab-derived fluids suggest extensive B-depletion during subduction, resulting in low-B, isotopically light compositions whereas kimberlite-related metasomatic products and a sample from the 2 Ga Palabora carbonatite have boron isotopic compositions similar to proposed primitive mantle. The results suggest that subduction of oceanic lithosphere plays a limited role in the B geochemistry of the convecting mantle.
ContributorsGuild, Meghan R (Author) / Hervig, Richard L (Thesis advisor) / Bell, David R. (Committee member) / Mcnamara, Allen (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Carbonaceous chondrites (CCs) present a unique opportunity for learning about the earliest organic chemistry that took place in our Solar System. The complex and diverse suite of meteoritic organic material is the result of multiple settings and physicochemical processes, including aqueous and thermal alteration. Though meteorites often inform origin-of-life discussions

Carbonaceous chondrites (CCs) present a unique opportunity for learning about the earliest organic chemistry that took place in our Solar System. The complex and diverse suite of meteoritic organic material is the result of multiple settings and physicochemical processes, including aqueous and thermal alteration. Though meteorites often inform origin-of-life discussions because they could have seeded early Earth with significant amounts of water and pre-biotic, organic material, their record of abiotic, aqueous, and organic geochemistry is of interest as well.

CC materials previously resided on asteroidal parent bodies, relic planetesimals of Solar System formation which never accreted enough material to develop long-lived, large-scale geological processes. These bodies were large enough, however, to experience some degree of heating due to the decay of radiogenic isotopes, and the meteorite record suggests the existence of 100-150 parent bodies which experienced varying degrees of thermal and aqueous alteration for the first several 10 Myr of Solar System history.

The first chapter of this dissertation reviews literature addressing aqueous alteration as an essential participant in parent body geochemistry, organic synthesis, or both (though papers which address both are rare). The second chapter is a published organic analysis of the soluble organic material of Bells, an unclassified type 2 chondrite. Analytical approaches to assess terrestrial contamination of meteorite samples are also reviewed in the first chapter to allow introduction in chapter 3 of kinetic modeling which rules out certain cases of contamination and constrains the timing of thermal and aqueous alteration. This is the first known application of isoleucine epimerization for either of these purposes. Chapter 4 is a kinetic study of D-allo-isoleucine epimerization to establish its behavior in systems with large, relative abundances of alloisoleucine to isoleucine. Previous epimerization studies for paleontological or geological purposes began with L-isoleucine, the only protein amino acid of the four isoleucine stereoisomers.

Kinetic model calculations using isoleucine stereoisomer abundances from 7 CR chondrites constrain the total duration of the amino acids' residence in the aqueous phase. The comparatively short timescales produced by the presented modeling elicit hypotheses for protection or transport of the amino acids within the CR parent body.
ContributorsMonroe, Adam Alexander (Author) / Pizzarello, Sandra (Thesis advisor) / Williams, Peter (Thesis advisor) / Anbar, Ariel D (Committee member) / Shock, Everett L (Committee member) / Arizona State University (Publisher)
Created2014
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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 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.
ContributorsBowman, Margaret (Author) / Hartnett, Hilairy E (Thesis advisor) / Hayes, Mark A. (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2015
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Description
The taxonomic and metabolic profile of the microbial community inhabiting a natural system is largely determined by the physical and geochemical properties of the system. However, the influences of parameters beyond temperature, pH and salinity have been poorly analyzed with few studies incorporating the comprehensive suite of physical and geochemical

The taxonomic and metabolic profile of the microbial community inhabiting a natural system is largely determined by the physical and geochemical properties of the system. However, the influences of parameters beyond temperature, pH and salinity have been poorly analyzed with few studies incorporating the comprehensive suite of physical and geochemical measurements required to fully investigate the complex interactions known to exist between biology and the environment. Further, the techniques used to classify the taxonomic and functional composition of a microbial community are fragmented and unwieldy, resulting in unnecessarily complex and often non-consilient results.

This dissertation integrates environmental metagenomes with extensive geochemical metadata for the development and application of multidimensional biogeochemical metrics. Analysis techniques including a Markov cluster-based evolutionary distance between whole communities, oligonucleotide signature-based taxonomic binning and principal component analysis of geochemical parameters allow for the determination of correlations between microbial community dynamics and environmental parameters. Together, these techniques allow for the taxonomic classification and functional analysis of the evolution of hot spring communities. Further, these techniques provide insight into specific geochemistry-biology interactions which enable targeted analyses of community taxonomic and functional diversity. Finally, analysis of synonymous substitution rates among physically separated microbial communities provides insights into microbial dispersion patterns and the roles of environmental geochemistry and community metabolism on DNA transfer among hot spring communities.

The data presented here confirms temperature and pH as the primary factors shaping the evolutionary trajectories of microbial communities. However, the integration of extensive geochemical metadata reveals new links between geochemical parameters and the distribution and functional diversification of communities. Further, an overall geochemical gradient (from multivariate analyses) between natural systems provides one of the most complete predictions of microbial community functional composition and inter-community DNA transfer rates. Finally, the taxonomic classification and clustering techniques developed within this dissertation will facilitate future genomic and metagenomic studies through enhanced community profiling obtainable via Markov clustering, longer oligonucleotide signatures and insight into PCR primer biases.
ContributorsAlsop, Eric Bennie (Author) / Raymond, Jason (Thesis advisor) / Anbar, Ariel (Committee member) / Farmer, Jack (Committee member) / Shock, Everett (Committee member) / Walker, Sarah (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The hydrothermal chemistry of organic compounds influences many critical geological processes, including the formation of oil and gas reservoirs, the degradation and transport of organic matter in sedimentary basins, metabolic cycles in the deep subsurface biosphere, and possibly prebiotic organic synthesis related to the origin of life. In most

The hydrothermal chemistry of organic compounds influences many critical geological processes, including the formation of oil and gas reservoirs, the degradation and transport of organic matter in sedimentary basins, metabolic cycles in the deep subsurface biosphere, and possibly prebiotic organic synthesis related to the origin of life. In most previous studies of hydrothermal organic reactions the emphasis has been mainly on determining reaction product distributions, studies that provide detailed mechanistic information or direct evidence for specific reaction intermediates are rare. To develop a better understanding, I performed hydrothermal experiments with model ketone compound dibenzylketone (DBK), which serves as a quite useful tool to probe the bond breaking and forming processes in hydrothermal geochemical transformations. A careful study of reaction kinetics and products of DBK in Chapter 2 of this dissertation reveals reversible and irreversible reaction pathways, and provides evidence for competing ionic and radical reaction mechanisms. The majority of the observed products result from homolytic carbon-carbon and carbon-hydrogen bond cleavage and secondary coupling reactions of the benzyl and related radical intermediates.

In the third chapter of the dissertation, a novel hydrothermal photochemical method is studied, which enabled in situ independent generation of the relevant radicals and effectively separated the radical and ionic reactions that occur simultaneously in pure thermal reactions. In the following chapter, I focus on the role of minerals on ketone hydrothermal reactions. Minerals such as quartz and corundum have no detectable effect on DBK, whereas magnetite, hematite, and troilite all increase ketone reactivity to various extents. The influence of these iron-bearing minerals can be attributed to the mineral surface catalysis or the solution chemistry change that is presumably caused by dissolved inorganic species from minerals. In addition, some new discoveries on strong oxidizing effect of copper (II) ion under hydrothermal conditions are described in the latter chapter of the dissertation, where examples of clean and rapid reactions that converted alcohols to aldehyde and aldehydes to carboxylic acids are included.
ContributorsYang, Ziming (Author) / Shock, Everett L (Thesis advisor) / Gould, Ian R (Committee member) / Wolf, George H. (Committee member) / Arizona State University (Publisher)
Created2014