Matching Items (21)
Filtering by
- All Subjects: Geochemistry
- Genre: Academic theses
- Creators: Hervig, Richard L
- Creators: Anbar, Ariel
- Member of: ASU Electronic Theses and Dissertations
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 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
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, 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
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 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
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 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.
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
Description
A new analytical method is proposed for measuring the deuterium to hydrogen ratio (D/H) of non-stoichiometric water in hydrous minerals via pyrolysis facilitated gas-chromatography - isotope ratio mass spectrometry (GC-IRMS). Previously published analytical methods have reported a poorly understood nonlinear dependence of D/H on sample size, for which any accurate correction is difficult. This sample size effect been variously attributed to kinetic isotope fractionation within the mass spectrometer and peripheral instruments, ion source linearity issues, and an unstable H_3^+-factor or incorrect H_3^+-factor calculations. The cause of the sample size effect is here identified by examinations of individual chromatograms as well as bulk data from chromatographic peaks. It is here determined that it is primarily an artifact of the calculations employed by the manufacturer's computer program, used to both monitor the functions of the mass spectrometer and to collect data. Ancillary causes of the sample size effect include a combination of persistent background interferences and chromatographic separation of the isotopologues of molecular hydrogen. Previously published methods are evaluated in light of these findings. A new method of H_3^+-factor and D/H calculation is proposed which makes portions of the Isodat software as well as other published calculation methods unnecessary. Using this new method, D/H is measured in non-stoichiometric water in chert from the Cretaceous Edwards Group, Texas, as well as the Precambrian Kromberg Formation, South Africa, to assess hydrological conditions as well as to estimate the maximum average surface temperature during precipitation of the chert. Data from Cretaceous chert are consistent with previously published data and interpretations, based upon conventional analyses of large samples. Data from Precambrian chert are consistent with maximum average surface temperatures approaching 65°C during the Archean, instead of the much lower temperatures derived from erroneous methods of sample preparation and analysis. D/H is likewise measured in non-stoichiometric water in silicified basalt from the Precambrian Hooggenoeg Complex, South Africa. Data are shown to be consistent with D/H of the Archean ocean similar to present day values.
ContributorsSheehan, Michael Robert (Author) / Knauth, Leroy P (Thesis advisor) / Anbar, Ariel (Committee member) / Farmer, Jack (Committee member) / Arizona State University (Publisher)
Created2011
Description
Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients, such as iron, copper, and molybdenum. This work investigated the effects of BSC activity on soil solution concentrations of bioessential elements and examined the microbial production of organic chelators, called siderophores. I found that aluminum, vanadium, copper, zinc, and molybdenum were solubilized in the action of crusts, while nickel, zinc, arsenic, and zirconium were immobilized by crust activity. Potassium and manganese displayed behavior consistent with biological removal and mobilization, whereas phosphorus and iron solubility were dominated by abiotic processes. The addition of bioavailable nitrogen altered the effects of BSCs on soil element mobilization. In addition, I found that the biogeochemical activites of BSCs were limited by molybdenum, a fact that likely contributes to co-limitation by nitrogen. I confirmed the presence of siderophore producing microbes in BSCs. Siderophores are low-molecular weight organic compounds that are released by bacteria to increase element solubility and facilitate element uptake; siderophore production is likely the mechanism by which BSCs affect the patterns I observed in soil solution element concentrations. Siderophore producers were distributed across a range of bacterial groups and ecological niches within crusts, suggesting that siderophore production influences the availability of a variety of elements for use in many physiological processes. Four putative siderophore compounds were identified using electrospray ionization mass spectrometry; further attempts to characterize the compounds confirmed two true siderophores. Taken together, the results of my work provide information about micronutrient cycling within crusts that can be applied to BSC conservation and management. Fertilization with certain elements, particularly molybdenum, may prove to be a useful technique to promote BSC growth and development which would help prevent arid land degradation. Furthermore, understanding the effects of BSCs on soil element mobility could be used to develop useful biomarkers for the study of the existence and distribution of crust-like communities on ancient Earth, and perhaps other places, like Mars.
ContributorsNoonan, Kathryn Alexander (Author) / Hartnett, Hilairy (Thesis advisor) / Anbar, Ariel (Committee member) / Garcia-Pichel, Ferran (Committee member) / Shock, Everett (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2012
Description
Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding of the diagenetic processes that may affect molybdenum and uranium isotopes entering the rock record. Using samples from the Black Sea water column, the first water column profile of 238U/235U variations from a modern euxinic basin has been measured. This profile allows the direct determination of the 238U/235U fractionation factor in a euxinic marine setting. More importantly however, these data demonstrate the extent of Rayleigh fractionation of U isotopes that can occur in euxinic restricted basins. Because of this effect, the offset of 238U/235U between global average seawater and coeval black shales deposited in restricted basins is expected to depend on the degree of local uranium drawdown from the water column, potentially complicating the interpretation 238U/235U paleorecords. As an alternative to the black shales typically used for paleoredox reconstructions, molybdenum and uranium isotope variations in bulk carbonate sediments from the Bahamas are examined. The focus of this work was to determine what processes, if any, fractionate molybdenum and uranium isotopes during incorporation into bulk carbonate sediments and their subsequent diagenesis. The results demonstrate that authigenic accumulation of molybdenum and uranium from anoxic and sulfidic pore waters is a dominant process controlling the concentration and isotopic composition of these sediments during early diagenesis. Examination of ODP drill core samples from the Bahamas reveals similar behavior for sediments during the first ~780ka of burial, but provides important examples where isolated cores and samples occasionally demonstrate additional fractionation, the cause of which remains poorly understood.
ContributorsRomaniello, Stephen J. (Author) / Anbar, Ariel (Thesis advisor) / Hartnett, Hilairy (Committee member) / Herrmann, Achim (Committee member) / Shock, Everett (Committee member) / Wadhwa, Meenakshi (Committee member) / Arizona State University (Publisher)
Created2012
Description
Fluorine (F) is a volatile constituent of magmas and hydrous mantle minerals. Compared to other volatile species, F is highly soluble in silicate melts, allowing F to remain in the melt during magma differentiation and rendering F less subject to disturbance during degassing upon magma ascent. Hence, the association between fluorine in basalts and fluorine in the mantle source region is more robust than for other volatile species. The ionic radius of F- is similar to that of OH- and O2-, and F may substitute for hydroxyl and oxygen in silicate minerals and melt. Fluorine is also incorporated at trace levels within nominally anhydrous minerals (NAMs) such as olivine, clinopyroxene, and plagioclase. Investigating the geochemical behavior of F in NAMs provides a means to estimate the pre-eruptive F contents of degassed magmas and to better understand the degassing behavior of H. The partition coefficients of F were determined for clinopyroxene, olivine, plagioclase, and hornblende within melts of olivine-minette, augite-minette, basaltic andesite, and latite compositions. The samples analyzed were run products from previously-published phase-equilibria experiments. Fluorine was measured by secondary ion mass spectrometry (SIMS) using an 16O- primary beam and detection of negative secondary ions (19F-, 18O-, 28Si-). SIMS ion intensities are converted to concentrations by analyzing matrix-matched microanalytical reference materials and constructing calibration curves. For robust F calibration standards, five basaltic glasses (termed Fba glasses) were synthesized in-house using a natural tholeiite mixed with variable amounts of CaF2. The Fba glasses were characterized for F content and homogeneity, using both SIMS and electron-probe microanalysis (EPMA), and used as F standards. The partition coefficients for clinopyroxene (0.04-028) and olivine (0.01-0.16) varied with melt composition such that DF (olivine-minette) < DF (augite-minette) < DF (basaltic andesite) < DF (latite). Crystal chemical controls were found to influence the incorporation of F into clinopyroxene, but none were found that affected olivine. Fluorine partitioning was compared with that of OH within clinopyroxenes, and the alumina content of clinopyroxene was shown to be a strong influence on the incorporation of both anions. Fluorine substitution into both olivine and clinopyroxene was found to be strongly controlled by melt viscosity and degree of melt polymerization.
ContributorsGuggino, Steve (Author) / Hervig, Richard L (Thesis advisor) / Donald, Burt M (Committee member) / Amanda, Clarke B (Committee member) / Lynda, Williams B (Committee member) / Stanley, Williams N (Committee member) / Arizona State University (Publisher)
Created2012
Description
Natural variations in 238U/235U of marine carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ~7.5 and ~ 8.5 to study possible U isotope fractionation during incorporation into these minerals.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
ContributorsChen, Xinming (Author) / Anbar, Ariel (Thesis advisor) / Herckes, Pierre (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2015
Description
There is a growing body of evidence that the evolving redox structure of the oceans has been an important influence on the evolutionary trajectory of animals. However, current understanding of connections between marine redox conditions and marine extinctions and recoveries is hampered by limited detailed knowledge of the timing, duration, and extent of marine redox changes.
The recent development of U isotopes (δ238U) in carbonates as a global ocean redox proxy has provided new insight into this problem. Reliable application and interpretation of the δ238U paleoproxy in geological records requires a thorough understanding of the reliability of δ238U recorded by bulk carbonate sediments. In this dissertation, I evaluate the robustness of δ238U paleoproxy by examining δ238U variations in marine carbonates across Permian-Triassic boundary (PTB) sections from different paleogeographic locations. Close agreement of δ238U profiles from coeval carbonate sections thousands of kilometers apart, in different ocean basins, and with different diagenetic histories, strongly suggests that bulk carbonate sediments can reliably preserve primary marine δ238U signals, validating the carbonate U-isotope proxy for global-ocean redox analysis.
To improve understanding of the role of marine redox in shaping the evolutionary trajectory of animals, high-resolution δ238U records were generated across several key evolutionary periods, including the Ediacaran-to-Early Cambrian Explosion of complex life (635-541 Ma) and the delayed Early Triassic Earth system recovery from the PTB extinction (252-246 Ma). Based on U isotope variations in the Ediacaran-to-the Early Cambrian ocean, the initial diversification of the Ediacara biota immediately postdates an episode of pervasive ocean oxygenation across the Shuram event. The subsequent decline and extinction of the Ediacara biota is coincident with an episode of extensive anoxic conditions during the latest Ediacaran Period. These findings suggest that global marine redox changes drove the rise and fall of the Ediacara biota. Based on U isotope variations, the Early Triassic ocean was characterized by multiple episodes of extensive marine anoxia. By comparing the high-resolution δ238U record with the sub-stage ammonoid extinction rate curve, it appears that multiple oscillations in marine anoxia modulated the recovery of marine ecosystems following the latest Permian mass extinction.
The recent development of U isotopes (δ238U) in carbonates as a global ocean redox proxy has provided new insight into this problem. Reliable application and interpretation of the δ238U paleoproxy in geological records requires a thorough understanding of the reliability of δ238U recorded by bulk carbonate sediments. In this dissertation, I evaluate the robustness of δ238U paleoproxy by examining δ238U variations in marine carbonates across Permian-Triassic boundary (PTB) sections from different paleogeographic locations. Close agreement of δ238U profiles from coeval carbonate sections thousands of kilometers apart, in different ocean basins, and with different diagenetic histories, strongly suggests that bulk carbonate sediments can reliably preserve primary marine δ238U signals, validating the carbonate U-isotope proxy for global-ocean redox analysis.
To improve understanding of the role of marine redox in shaping the evolutionary trajectory of animals, high-resolution δ238U records were generated across several key evolutionary periods, including the Ediacaran-to-Early Cambrian Explosion of complex life (635-541 Ma) and the delayed Early Triassic Earth system recovery from the PTB extinction (252-246 Ma). Based on U isotope variations in the Ediacaran-to-the Early Cambrian ocean, the initial diversification of the Ediacara biota immediately postdates an episode of pervasive ocean oxygenation across the Shuram event. The subsequent decline and extinction of the Ediacara biota is coincident with an episode of extensive anoxic conditions during the latest Ediacaran Period. These findings suggest that global marine redox changes drove the rise and fall of the Ediacara biota. Based on U isotope variations, the Early Triassic ocean was characterized by multiple episodes of extensive marine anoxia. By comparing the high-resolution δ238U record with the sub-stage ammonoid extinction rate curve, it appears that multiple oscillations in marine anoxia modulated the recovery of marine ecosystems following the latest Permian mass extinction.
ContributorsZhang, Feifei (Author) / Anbar, Ariel (Thesis advisor) / Gordon, Gwyneth (Committee member) / Hartnett, Hilairy (Committee member) / Wadhwa, Meenakshi (Committee member) / Ruff, Steven (Committee member) / Arizona State University (Publisher)
Created2018