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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
Historically, uranium has received intense study of its chemical and isotopic properties for use in the nuclear industry, but has been largely ignored by geoscientists despite properties that make it an intriguing target for geochemists and cosmochemists alike. Uranium was long thought to have an invariant 238U/235U ratio in natural

Historically, uranium has received intense study of its chemical and isotopic properties for use in the nuclear industry, but has been largely ignored by geoscientists despite properties that make it an intriguing target for geochemists and cosmochemists alike. Uranium was long thought to have an invariant 238U/235U ratio in natural samples, making it uninteresting for isotopic work. However, recent advances in mass spectrometry have made it possible to detect slight differences in the 238U/235U ratio, creating many exciting new opportunities for U isotopic research. Using uranium ore samples from diverse depositional settings from around the world, it is shown that the low-temperature redox transition of uranium (U6+ to U4+) causes measurable fractionation of the 238U/235U ratio. Moreover, it is shown experimentally that a coordination change of U can also cause measurable fractionation in the 238U/235U ratio. This improved understanding of the fractionation mechanisms of U allows for the use of the 238U/235U ratio as a paleoredox proxy. The 238U/235U ratios of carbonates deposited spanning the end-Permian extinction horizon provide evidence of pronounced and persistent widespread ocean anoxia at, or immediately preceding, the extinction boundary. Variable 238U/235U ratios correlated with proxies for initial Cm/U in the Solar System's earliest objects demonstrates the existence of 247Cm in the early Solar System. Proof of variable 238U/235U ratios in meteoritic material forces a substantive change in the previously established procedures of Pb-Pb dating, which assumed an invariant 238U/235U ratio. This advancement improves the accuracy of not only the Pb-Pb chronometer that directly utilizes the 238U/235U ratio, but also for short-lived radiometric dating techniques that indirectly use the 238U/235U ratio to calculate ages of Solar System material.
ContributorsBrennecka, Gregory A (Author) / Anbar, Ariel D (Thesis advisor) / Wadhwa, Meenakshi (Thesis advisor) / Herrmann, Achim D (Committee member) / Hervig, Richard (Committee member) / Young, Patrick (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are

Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are essential for interpreting Martian mineralogy and geologic history. However, previous studies have shown that chemical weathering and the precipitation of fine-grained secondary silicates can adversely affect the accuracy of TIR spectral models. Furthermore, spectral libraries used to identify minerals on the Martian surface lack some important weathering products, including poorly-crystalline aluminosilicates like allophane, thus eliminating their identification in TIR spectral models. It is essential to accurately interpret TIR spectral data from chemically weathered surfaces to understand the evolution of aqueous processes on Mars. Laboratory experiments were performed to improve interpretations of TIR data from weathered surfaces. To test the accuracy of deriving chemistry of weathered rocks from TIR spectroscopy, chemistry was derived from TIR models of weathered basalts from Baynton, Australia and compared to actual weathering rind chemistry. To determine how specific secondary silicates affect the TIR spectroscopy of weathered basalts, mixtures of basaltic minerals and small amounts of secondary silicates were modeled. Poorly-crystalline aluminosilicates were synthesized and their TIR spectra were added to spectral libraries. Regional Thermal Emission Spectrometer (TES) data were modeled using libraries containing these poorly-crystalline aluminosilicates to test for their presence on the Mars. Chemistry derived from models of weathered Baynton basalts is not accurate, but broad chemical weathering trends can be interpreted from the data. TIR models of mineral mixtures show that small amounts of crystalline and amorphous silicate weathering products (2.5-5 wt.%) can be detected in TIR models and can adversely affect modeled plagioclase abundances. Poorly-crystalline aluminosilicates are identified in Northern Acidalia, Solis Planum, and Meridiani. Previous studies have suggested that acid sulfate weathering was the dominant surface alteration process for the past 3.5 billion years; however, the identification of allophane indicates that alteration at near-neutral pH occurred on regional scales and that acid sulfate weathering is not the only weathering process on Mars.
ContributorsRampe, Elizabeth Barger (Author) / Sharp, Thomas G (Thesis advisor) / Christensen, Phillip (Committee member) / Hervig, Richard (Committee member) / Shock, Everett (Committee member) / Williams, Lynda (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Understanding the evolution of the Himalayan-Tibetan orogen is important because of its purported effects on global geodynamics, geochemistry and climate. It is surprising that the timing of initiation of this canonical collisional orogen is poorly constrained, with estimates ranging from Late Cretaceous to Early Oligocene. This study focuses on the

Understanding the evolution of the Himalayan-Tibetan orogen is important because of its purported effects on global geodynamics, geochemistry and climate. It is surprising that the timing of initiation of this canonical collisional orogen is poorly constrained, with estimates ranging from Late Cretaceous to Early Oligocene. This study focuses on the Ladakh region in the northwestern Indian Himalaya, where early workers suggested that sedimentary deposits of the Indus Basin molasse sequence, located in the suture zone, preserve a record of the early evolution of orogenesis, including initial collision between India and Eurasia. Recent studies have challenged this interpretation, but resolution of the issue has been hampered by poor accessibility, paucity of robust depositional age constraints, and disputed provenance of many units in the succession. To achieve a better understanding of the stratigraphy of the Indus Basin, multispectral remote sensing image analysis resulted in a new geologic map that is consistent with field observations and previously published datasets, but suggests a substantial revision and simplification of the commonly assumed stratigraphic architecture of the basin. This stratigraphic framework guided a series of new provenance studies, wherein detrital U-Pb geochronology, 40Ar/39Ar and (U-Th)/He thermochronology, and trace-element geochemistry not only discount the hypothesis that collision began in the Early Oligocene, but also demonstrate that both Indian and Eurasian detritus arrived in the basin prior to deposition of the last marine limestone, constraining the age of collision to older than Early Eocene. Detrital (U-Th)/He thermochronology further elucidates the thermal history of the basin. Thus, we constrain backthrusting, thought to be an important mechanism by which Miocene convergence was accommodated, to between 11-7 Ma. Finally, an unprecedented conventional (U-Th)/He thermochronologic dataset was generated from a modern river sand to assess steady state assumptions of the source region. Using these data, the question of the minimum number of dates required for robust interpretation was critically evaluated. The application of a newly developed (U-Th)/He UV-laser-microprobe thermochronologic technique confirmed the results of the conventional dataset. This technique improves the practical utility of detrital mineral (U-Th)/He thermochronology, and will facilitate future studies of this type.
ContributorsTripathy, Alka (Author) / Hodges, Kip V (Thesis advisor) / Semken, Steven (Committee member) / Van Soest, Matthijs C (Committee member) / Whipple, Kelin X (Committee member) / Christensen, Philip R. (Philip Russel) (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines

Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines the fidelity of 238U/235U in sedimentary carbonate rocks as a paleoredox proxy focusing on the following issues: (1) U isotope fractionation during U incorporation into primary abiotic and biogenic calcium carbonates; (2) diagenetic effects on U isotope fractionation in modern shallow-water carbonate sediments; (3) the effects of anoxic depositional environments on 238U/235U in carbonate sediments.

Variable and positive shifts of 238U/235U were observed during U uptake by primary abiotic and biotic calcium carbonates, carbonate diagenesis, and anoxic deposition of carbonates. Previous CaCO3 coprecipitation experiments demonstrated a small but measurable U isotope fractionation of ~0.10 ‰ during U(VI) incorporation into abiotic calcium carbonates, with 238U preferentially incorporated into the precipitates (Chen et al., 2016). The magnitude of U isotope fractionation depended on aqueous U speciation, which is controlled by water chemistry, including pH, ionic strength, carbonate, and Ca2+ and Mg2+ concentrations. Based on this speciation-dependent isotope fractionation model, the estimated U isotope fractionation in abiotic calcium carbonates induced by secular changes in seawater chemistry through the Phanerozoic was predicted to be 0.11–0.23 ‰. A smaller and variable U isotope fractionation (0–0.09 ‰) was observed in primary biogenic calcium carbonates, which fractionated U isotopes in the same direction as abiotic calcium carbonates. Early diagenesis of modern shallow-water carbonate sediments from the Bahamas shifted δ238U values to be 0.270.14 ‰ (1 SD) higher than contemporaneous seawater. Also, carbonate sediments deposited under anoxic conditions in a redox-stratified lake—Fayetteville Green Lake, New York, USA— exhibited elevated δ238U values by 0.160.12 ‰ (1 SD) relative to surface water carbonates with significant enrichments in U.

The significant U isotope fractionation observed in these studies suggests the need to correct for the U isotopic offset between carbonate sediments and coeval seawater when using δ238U variations in ancient carbonate rocks to reconstruct changes in ocean anoxia. The U isotope fractionation in abiotic and biogenic primary carbonate precipitates, during carbonate diagenesis, and under anoxic depositional environments provide a preliminary guideline to calibrate 238U/235U in sedimentary carbonate rocks as a paleoredox proxy.
ContributorsChen, Xinming (Author) / Anbar, Ariel D (Thesis advisor) / Williams, Lynda B (Committee member) / Sharp, Thomas (Committee member) / Hervig, Richard (Committee member) / Romaniello, Stephen (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Among volcanic gases, sulfur dioxide (SO2) is by far the most commonly measured. More than a monitoring proxy for volcanic degassing, SO2 has the potential to alter climate patterns. Persistently active explosive volcanoes are characterized by short explosive bursts, which often occur at periodic intervals numerous times per day,

Among volcanic gases, sulfur dioxide (SO2) is by far the most commonly measured. More than a monitoring proxy for volcanic degassing, SO2 has the potential to alter climate patterns. Persistently active explosive volcanoes are characterized by short explosive bursts, which often occur at periodic intervals numerous times per day, spanning years to decades. SO2 emissions at those volcanoes are poorly constrained, in large part because the current satellite monitoring techniques are unable to detect or quantify plumes of low concentration in the troposphere. Eruption plumes also often show high concentrations of ash and/or aerosols, which further inhibit the detection methods. In this work I focus on quantifying volcanic gas emissions at persistently active explosive volcanoes and their variations over short timescales (minutes to hours), in order to document their contribution to natural SO2 flux as well as investigate the physical processes that control their behavior.

In order to make these measurements, I first develop and assemble a UV ground-based instrument, and validate it against an independently measured source of SO2 at a coal-burning power plant in Arizona. I establish a measurement protocol and demonstrate that the instrument measures SO2 fluxes with < 20 % error. Using the same protocol, I establish a record of the degassing patterns at Semeru volcano (Indonesia), a volcano that has been producing cycles of repeated explosions with periods of minutes to hours for the past several decades. Semeru produces an average of 21-71 tons of SO2 per day, amounting to a yearly output of 8-26 Mt.

Using the Semeru data, along with a 1-D transient numerical model of magma ascent, I test the validity of a model in which a viscous plug at the top of the conduit produces cycles of eruption and gas release. I find that it can be a valid hypothesis to explain the observed patterns of degassing at Semeru. Periodic behavior in such a system occurs for a very narrow range of conditions, for which the mass balance between magma flux and open-system gas escape repeatedly generates a viscous plug, pressurizes the magma beneath the plug, and then explosively disrupts it.
ContributorsSmekens, Jean-François (Author) / Clarke, Amanda (Thesis advisor) / Christensen, Philip R. (Philip Russel) (Committee member) / Williams, Stanley (Committee member) / Burton, Michael (Committee member) / Fink, Jonathan (Committee member) / Moore, Gordon (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so the unambiguous identification of these phases is important for understanding

Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so the unambiguous identification of these phases is important for understanding the geologic history of Mars. Secondary amorphous silicates are poorly understood and underrepresented in spectral libraries because they lack the long-range structural order that makes their crystalline counterparts identifiable in most analytical techniques. Fortunately, even amorphous materials have some degree of short-range order so that distinctions can be made with careful characterization.

Two sets of laboratory experiments were used to produce and characterize amorphous weathering products under probable conditions for the Martian surface, and one global spectral analysis using thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) instrument was used to constrain variations in amorphous silicates across the Martian surface. The first set of experiments altered crystalline and glassy basalt samples in an open system under strong (pH 1) and moderate (pH 3) acidic conditions. The second set of experiments simulated a current-day Martian weathering scenario involving transient liquid water where basalt glass weathering solutions, formed in circumneutral (pH ~5.5 and 7) conditions, were rapidly evaporated, precipitating amorphous silicates. The samples were characterized using visible and near-infrared (VNIR) spectroscopy, TIR spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD).

All experiments formed amorphous silicate phases that are new to spectral libraries. Moderately acidic alteration experiments produced no visible or spectral evidence of alteration products, whereas exposure of basalt glass to strongly acidic fluids produced silica-rich alteration layers that are spectrally consistent with VNIR and TIR spectra from the circum-polar region of Mars, indicating this region has undergone acidic weathering. Circum-netural pH basalt weathering solution precipitates are consistent with amorphous materials measured by rovers in soil and rock surface samples in Gale and Gusev Craters, suggesting transient water interactions over the last 3 billion years. Global spectral analyses determine that alteration conditions have varied across the Martian surface, and that alteration has been long lasting.
ContributorsSmith, Rebecca (Author) / Christensen, Philip R. (Philip Russel) (Thesis advisor) / Shock, Everett (Committee member) / Hartnett, Hilairy (Committee member) / Shim, Sang-Heon (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The Kilopixel Array Pathfinder Project (KAPPa) advances the number of coherent high-frequency terahertz (THz) receivers that could be packed into a single focal plane array on existing submm telescopes. The KAPPa receiver, at 655-695 GHz, is a high frequency heterodyne receiver that can achieve system temperatures of less than 200

The Kilopixel Array Pathfinder Project (KAPPa) advances the number of coherent high-frequency terahertz (THz) receivers that could be packed into a single focal plane array on existing submm telescopes. The KAPPa receiver, at 655-695 GHz, is a high frequency heterodyne receiver that can achieve system temperatures of less than 200 K, the specification for ALMA band-9. The KAPPa receiver uses a novel design of a permanent magnet to suppress the noise generated by the DC Josephson effect. This is in stark contrast to the benchmark solution of an electromagnet that is both too expensive and too large for use in kilo-pixel arrays. I present a simple, robust design for a single receiver element that can be tessellated throughout a telescope's focal plane to make a ~1000 pixel array, which is much larger than the current state-of-the-art array, SuperCam, at 64 pixels and ~345 GHz.

While the original goal to develop receiver technologies has been accomplished, the path to this accomplishment required a far more holistic approach than originally anticipated. The goal of the present work has expended exponentially from that of KAPPas promised technical achievements. In the present work, KAPPa and its extension, I present solutions ranging from 1) the creation of large scale astronomical maps, 2) metaheuristic algorithms that solve tasks too complex for humans, and 3) detailed technical assembly of microscopic circuit components. Each part is equally integral for the realization of a ~1000 pixel THz arrays.

Our automated tuning algorithm, Alice, uses differential evolution techniques and has been extremely successful in its implementation. Alice provides good results for characterizing the extremely complex tuning topology of THz receivers. More importantly, it has accomplished rapid optimization of an entire array without human intervention. In the age of big data astronomy, I have prepared THz heterodyne receiver arrays by making cutting edge community-oriented data analysis tools for the future of large-scale discovery. I present a from-scratch reduction and analysis architecture developed for observations of 100s of square degree on-the-sky maps with SuperCam to address the gulf between observing with single dish antennas versus a truly integrated focal plane array.
ContributorsWheeler, Caleb Henry, III (Author) / Groppi, Christopher E (Thesis advisor) / Butler, Nathaniel (Committee member) / Christensen, Philip R. (Philip Russel) (Committee member) / Mauskopf, Philip (Committee member) / Scowen, Paul (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The beginning of our Solar System, including events such as the formation of the first solids as well as the accretion and differentiation of planetary bodies, is recorded in meteoritic material. This record can be deciphered using petrographic, geochemical and isotopic investigations of different classes of meteorites and their components.

The beginning of our Solar System, including events such as the formation of the first solids as well as the accretion and differentiation of planetary bodies, is recorded in meteoritic material. This record can be deciphered using petrographic, geochemical and isotopic investigations of different classes of meteorites and their components. In this dissertation, I have investigated a variety of isotope systematics in chondritic and achondritic meteorites to understand processes that have shaped our Solar System. Specifically, the investigations conducted here are in two main areas: 1) Hydrogen isotope systematics in a meteorite representing the freshest known sample of the martian crust, and 2) Isotopic studies (specifically relating to high resolution chronology, nucleosynthetic anomalies and mass-dependent fractionations) in calcium-aluminum-rich inclusions, which are thought to be the earliest-formed solids in the Solar System. Chapter 1 of this dissertation presents a review of the hydrogen isotopic compositions of various planetary bodies and reservoirs in the Solar System, which could serve as tracers for the volatile sources. Chapter 2 focuses on an investigation of the hydrogen isotopic systematics in the freshest martian meteorite fall, Tissint, using the Cameca IMS-6f secondary ion mass spectrometer (SIMS). These first two chapters comprise the first part of this dissertation. The second part is comprised of chapters 3 through 6 and is focused on isotopic analyses of Calcium-Aluminum-rich Inclusions (CAIs). Chapter 3 is a review of CAIs, which record some of the earliest processes that occurred in the solar nebula. Chapter 4 presents the results of an investigation of the 26Al-26Mg short-lived chronometer (half-life ~0.72 Ma) in two CAIs and their Wark-Lovering (WL) rims from a CV3 carbonaceous chondrite using the Cameca NanoSIMS 50L. Chapter 5 is focused on the results of a study of the Zr isotope compositions of a suite of 15 CAIs from different carbonaceous chondrites using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), in order to identify nucleosynthetic anomalies in the CAI-forming region. Chapter 6 focuses on the mass-dependent Mg isotopic compositions measured in 11 CAIs from the Allende CV3 carbonaceous chondrite using MC-ICPMS, to evaluate effects of thermal processing on CAIs.
ContributorsMane, Prajkta (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Desch, Steven (Committee member) / Garvie, Laurence (Committee member) / Bell, James (Committee member) / Arizona State University (Publisher)
Created2016