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- All Subjects: Geochemistry
- Creators: Anbar, Ariel D
- Status: Published
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 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.
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
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 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
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
Atmospheric deposition of iron (Fe) can limit primary productivity and carbon dioxide uptake in some marine ecosystems. Recent modeling studies suggest that biomass burning aerosols may contribute a significant amount of soluble Fe to the surface ocean. Existing studies of burn-induced trace element mobilization have often collected both entrained soil particles along with material from biomass burning, making it difficult to determine the actual source of aerosolized trace metals.
In order to better constrain the importance of biomass versus entrained soil as a source of trace metals in burn aerosols, small-scale burn experiments were conducted using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped with an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS).
Results of this analysis show that less than 2% of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events. The results of this study and estimates of annual global wildfire area were used to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. I estimate that foliage-derived Fe contributes 114 ± 57 Gg annually. Prior studies, which implicitly include both biomass and soil-derived Fe, concluded that biomass burning contributes approximately 690 Gg of Fe. Together, these studies suggest that fire-entrained soil particles contribute 83% (576 Gg) of Fe in biomass burning emissions, while plant derived iron only accounts for at most 17%.
In order to better constrain the importance of biomass versus entrained soil as a source of trace metals in burn aerosols, small-scale burn experiments were conducted using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped with an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS).
Results of this analysis show that less than 2% of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events. The results of this study and estimates of annual global wildfire area were used to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. I estimate that foliage-derived Fe contributes 114 ± 57 Gg annually. Prior studies, which implicitly include both biomass and soil-derived Fe, concluded that biomass burning contributes approximately 690 Gg of Fe. Together, these studies suggest that fire-entrained soil particles contribute 83% (576 Gg) of Fe in biomass burning emissions, while plant derived iron only accounts for at most 17%.
ContributorsSherry, Alyssa M (Author) / Anbar, Ariel D (Thesis advisor) / Herckes, Pierre (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2019
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 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 0.270.14 ‰ (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 0.160.12 ‰ (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.
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 0.270.14 ‰ (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 0.160.12 ‰ (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
Description
In this study, the influence of fluid mixing on temperature and geochemistry of hot spring fluids is investigated. Yellowstone National Park (YNP) is home to a diverse range of hot springs with varying temperature and chemistry. The mixing zone of interest in this paper, located in Geyser Creek, YNP, has been a point of interest since at least the 1960’s (Raymahashay, 1968). Two springs, one basic (~pH 7) and one acidic (~pH 3) mix together down an outflow channel. There are visual bands of different photosynthetic pigments which suggests the creation of temperature and chemical gradients due to the fluids mixing. In this study, to determine if fluid mixing is driving these changes of temperature and chemistry in the system, a model that factors in evaporation and cooling was developed and compared to measured temperature and chemical data collected downstream. Comparison of the modeled temperature and chemistry to the measured values at the downstream mixture shows that many of the ions, such as Cl⁻, F⁻, and Li⁺, behave conservatively with respect to mixing. This indicates that the influence of mixing accounts for a large proportion of variation in the chemical composition of the system. However, there are some chemical constituents like CH₄, H₂, and NO₃⁻, that were not conserved, and the concentrations were either depleted or increased in the downstream mixture. Some of these constituents are known to be used by microorganisms. The development of this mixing model can be used as a tool for predicting biological activity as well as building the framework for future geochemical and computational models that can be used to understand the energy availability and the microbial communities that are present.
ContributorsOrrill, Brianna Isabel (Author) / Shock, Everett (Thesis director) / Howells, Alta (Committee member) / School of Life Sciences (Contributor) / School of Earth and Space Exploration (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
Finding habitable worlds is a key driver of solar system exploration. Many solar
system missions seek environments providing liquid water, energy, and nutrients, the three ingredients necessary to sustain life.
Such environments include hydrothermal systems, spatially-confined systems where hot aqueous fluid circulates through rock by convection. I sought to characterize hydrothermal microbial communities, collected in hot spring sediments and mats at Yellowstone National Park, USA, by measuring their bulk elemental composition. To do so, one must minimize the contribution of non-biological material to the samples analyzed. I demonstrate that this can be achieved using a separation method that takes advantage of the density contrast between cells and sediment and preserves cellular elemental contents. Using this method, I show that in spite of the tremendous physical, chemical, and taxonomic diversity of Yellowstone hot springs, the composition of microorganisms there is surprisingly ordinary. This suggests the existence of a stoichiometric envelope common to all life as we know it. Thus, future planetary investigations could use elemental fingerprints to assess the astrobiological potential of hydrothermal settings beyond Earth.
Indeed, hydrothermal activity may be widespread in the solar system. Most solar system worlds larger than 200 km in radius are dwarf planets, likely composed of an icy, cometary mantle surrounding a rocky, chondritic core. I enhance a dwarf planet evolution code, including the effects of core fracturing and hydrothermal circulation, to demonstrate that dwarf planets likely have undergone extensive water-rock interaction. This supports observations of aqueous products on their surfaces. I simulate the alteration of chondritic rock by pure water or cometary fluid to show that aqueous alteration feeds back on geophysical evolution: it modifies the fluid antifreeze content, affecting its persistence over geological timescales; and the distribution of radionuclides, whose decay is a chief heat source on dwarf planets. Interaction products can be observed if transported to the surface. I simulate numerically how cryovolcanic transport is enabled by primordial and hydrothermal volatile exsolution. Cryovolcanism seems plausible on dwarf planets in light of images recently returned by spacecrafts. Thus, these coupled geophysical-geochemical models provide a comprehensive picture of dwarf planet evolution, processes, and habitability.
system missions seek environments providing liquid water, energy, and nutrients, the three ingredients necessary to sustain life.
Such environments include hydrothermal systems, spatially-confined systems where hot aqueous fluid circulates through rock by convection. I sought to characterize hydrothermal microbial communities, collected in hot spring sediments and mats at Yellowstone National Park, USA, by measuring their bulk elemental composition. To do so, one must minimize the contribution of non-biological material to the samples analyzed. I demonstrate that this can be achieved using a separation method that takes advantage of the density contrast between cells and sediment and preserves cellular elemental contents. Using this method, I show that in spite of the tremendous physical, chemical, and taxonomic diversity of Yellowstone hot springs, the composition of microorganisms there is surprisingly ordinary. This suggests the existence of a stoichiometric envelope common to all life as we know it. Thus, future planetary investigations could use elemental fingerprints to assess the astrobiological potential of hydrothermal settings beyond Earth.
Indeed, hydrothermal activity may be widespread in the solar system. Most solar system worlds larger than 200 km in radius are dwarf planets, likely composed of an icy, cometary mantle surrounding a rocky, chondritic core. I enhance a dwarf planet evolution code, including the effects of core fracturing and hydrothermal circulation, to demonstrate that dwarf planets likely have undergone extensive water-rock interaction. This supports observations of aqueous products on their surfaces. I simulate the alteration of chondritic rock by pure water or cometary fluid to show that aqueous alteration feeds back on geophysical evolution: it modifies the fluid antifreeze content, affecting its persistence over geological timescales; and the distribution of radionuclides, whose decay is a chief heat source on dwarf planets. Interaction products can be observed if transported to the surface. I simulate numerically how cryovolcanic transport is enabled by primordial and hydrothermal volatile exsolution. Cryovolcanism seems plausible on dwarf planets in light of images recently returned by spacecrafts. Thus, these coupled geophysical-geochemical models provide a comprehensive picture of dwarf planet evolution, processes, and habitability.
ContributorsNeveu, Marc François Laurent (Author) / Desch, Steven J (Thesis advisor) / Anbar, Ariel D (Thesis advisor) / Shock, Everett L (Committee member) / Elser, James J (Committee member) / McNamara, Allen K (Committee member) / Arizona State University (Publisher)
Created2015
Modelling Geochemical and Geobiological Consequences of Low-Temperature Continental Serpentinization
Description
The hydrous alteration of ultramafic rocks, known as serpentinization, produces some of the most reduced (H2 >1 mmolal) and alkaline (pH >11) fluids on Earth. Serpentinization can proceed even at the low-temperature conditions (<50°C) characteristic of most of Earth’s continental aquifers, raising questions on the limits of life deep in the subsurface and the magnitude in the flux of reduced volatiles to the surface. In this work, I explored the compositions and consequences of fluids and volatiles found in three low-temperature serpentinizing environments: (1) active hyperalkaline springs in ophiolites, (2) modern shallow and deep peridotite aquifers, and (3) komatiitic aquifers during the Archean.
Around 140 fluids were sampled from the Oman ophiolite and analyzed for their compositions. Fluid compositions can be accounted for by thermodynamic simulations of reactions accompanying incipient to advanced stages of serpentinization, as well as by simulations of mass transport processes such as fluid mixing and mineral leaching. Thermodynamic calculations were also used to predict compositions of end-member fluids representative of the shallow and deep peridotite aquifers that were ultimately used to quantify energy available to various subsurface chemolithotrophs. Calculations showed that sufficient energy and power supply can be available to support deep-seated methanogens. An additional and a more diverse energy supply can be available when surfacing deep-seated fluids mix with shallow groundwater in discharge zones of the subsurface fluid pathway. Finally, the consequence of the evolving continental composition during the Archean for the global supply of H2 generated through komatiite serpentinization was quantified. Results show that the flux of serpentinization-generated H2 could have been a significant sink for O2 during most of the Archean. This O2 sink diminished greatly towards the end of the Archean as komatiites became less common and helped set the stage for the Great Oxidation Event. Overall, this study provides a framework for exploring the origins of fluid and volatile compositions, including their redox state, that can result from various low-temperature serpentinizing environments in the present and past Earth and in other rocky bodies in the solar system.
Around 140 fluids were sampled from the Oman ophiolite and analyzed for their compositions. Fluid compositions can be accounted for by thermodynamic simulations of reactions accompanying incipient to advanced stages of serpentinization, as well as by simulations of mass transport processes such as fluid mixing and mineral leaching. Thermodynamic calculations were also used to predict compositions of end-member fluids representative of the shallow and deep peridotite aquifers that were ultimately used to quantify energy available to various subsurface chemolithotrophs. Calculations showed that sufficient energy and power supply can be available to support deep-seated methanogens. An additional and a more diverse energy supply can be available when surfacing deep-seated fluids mix with shallow groundwater in discharge zones of the subsurface fluid pathway. Finally, the consequence of the evolving continental composition during the Archean for the global supply of H2 generated through komatiite serpentinization was quantified. Results show that the flux of serpentinization-generated H2 could have been a significant sink for O2 during most of the Archean. This O2 sink diminished greatly towards the end of the Archean as komatiites became less common and helped set the stage for the Great Oxidation Event. Overall, this study provides a framework for exploring the origins of fluid and volatile compositions, including their redox state, that can result from various low-temperature serpentinizing environments in the present and past Earth and in other rocky bodies in the solar system.
ContributorsLeong, James Andrew (Author) / Shock, Everett L (Thesis advisor) / Anbar, Ariel D (Committee member) / Hartnett, Hilairy E (Committee member) / Sharp, Thomas G (Committee member) / Till, Christy B. (Committee member) / Arizona State University (Publisher)
Created2020
Description
Meteorites and their components can be used to unravel the history of the early Solar System. Carbonaceous chondrites are meteorites that originated from undifferentiated parent bodies that formed within a few million years of the beginning of the Solar System. These meteorites contain calcium-aluminum-rich inclusions (CAIs), which are the oldest dated solids in the Solar System at ~4.567 billion years old and thus preserve a record of the earliest stage of Solar System formation. The isotopic compositions of CAIs and bulk carbonaceous chondrites can be used to identify the sources of material inherited by the protoplanetary disk, assess the degree of mixing in the disk, and evaluate sample origins and potential genetic relationships between parent bodies. In particular, mass-independent Cr and Ti isotopic compositions have proven to be especially useful for these purposes.
In this work, I first developed new methods for the chemical separation of Cr and Ti, improving the reliability of existing methods to ensure consistent yields and accurate isotopic measurements. I then measured the Cr and Ti isotopic compositions of CAIs from CV and CK chondrites to determine the extent of isotopic heterogeneity in the CAI-forming region and assess the role of CAIs in the preservation of planetary-scale isotopic anomalies. My results show that all measured CAIs originated from a common isotopic reservoir that incorporated material from at least three distinct nucleosynthetic sources and preserved limited isotopic heterogeneity. These results also suggest that planetary-scale isotopic anomalies cannot be attributed solely to the transport of CAIs from one part of the solar nebula to another. I finally measured the Cr and Ti isotopic compositions of bulk CM, CO, and ungrouped chondrites to evaluate the relationship between CM and CO chondrites, which have been suggested to originate from either distinct but related parent bodies or a common compositionally heterogeneous parent body. My results suggest that CM, CO, and related ungrouped chondrites originated from distinct parent bodies that formed from similar precursor materials in nearby formation regions. These results may have implications for asteroid samples returned by the OSIRIS-REx and Hayabusa2 missions.
In this work, I first developed new methods for the chemical separation of Cr and Ti, improving the reliability of existing methods to ensure consistent yields and accurate isotopic measurements. I then measured the Cr and Ti isotopic compositions of CAIs from CV and CK chondrites to determine the extent of isotopic heterogeneity in the CAI-forming region and assess the role of CAIs in the preservation of planetary-scale isotopic anomalies. My results show that all measured CAIs originated from a common isotopic reservoir that incorporated material from at least three distinct nucleosynthetic sources and preserved limited isotopic heterogeneity. These results also suggest that planetary-scale isotopic anomalies cannot be attributed solely to the transport of CAIs from one part of the solar nebula to another. I finally measured the Cr and Ti isotopic compositions of bulk CM, CO, and ungrouped chondrites to evaluate the relationship between CM and CO chondrites, which have been suggested to originate from either distinct but related parent bodies or a common compositionally heterogeneous parent body. My results suggest that CM, CO, and related ungrouped chondrites originated from distinct parent bodies that formed from similar precursor materials in nearby formation regions. These results may have implications for asteroid samples returned by the OSIRIS-REx and Hayabusa2 missions.
ContributorsTorrano, Zachary (Author) / Wadhwa, Meenakshi (Thesis advisor) / Anbar, Ariel D (Committee member) / Schrader, Devin L (Committee member) / Williams, David A. (Committee member) / Young, Patrick A (Committee member) / Arizona State University (Publisher)
Created2020
Description
Isotope ratios of some trace metals have proven useful for tracking Earth’s ocean oxygenation history. As the limitations of some of these isotope systems are realized, it becomes increasingly important to develop new and complementary systems. This dissertation examines the utility of molybdenum (98Mo) and thallium (205Tl) isotope compositions preserved in ancient marine shales to track past ocean oxygenation. My approach is as follows: (1) as an initial exercise, apply the well-established Mo isotope system to a set of ancient shales; (2) validate the use of the newly developed Tl isotope system; and finally (3) examine the potential of applying Mo and Tl isotopes in tandem.
Increasingly heavier 98Mo are found in shales deposited during the Neoarchean (2,800 to 2,500 million years ago, or Ma), which would be a predicted consequence of progressive ocean oxygenation across this timeframe. Increasingly heavier 205Tl across a well-documented Mesozoic Oceanic Anoxic Event (~94 Ma), on the other hand, would be a predicted consequence of progressive ocean de-oxygenation. An anti-correlation in the first combined application of Mo and Tl isotopes in ancient shales provides a strong fingerprint for previously unrecognized levels of ocean oxygenation at ~2,500 Ma. Lastly, neither 98Mo or 205Tl behave as predicted in shales deposited during three Ediacaran Ocean Oxygenation Events (~635 Ma, ~580 Ma, and ~560 Ma). These unexpected trends are due, at least in part, to local-scale overprints that must be taken into consideration when pairing together Mo and Tl isotopes in shales.
The ability of the Mo and Tl isotope systems to track changes in past ocean oxygenation is confirmed in this dissertation. Both isotope systems have the potential to track these changes independently, but their combined utility is particularly powerful. Under ideal conditions, their combined application can provide an even more robust fingerprint for changes in past ocean oxygenation. Even under non-ideal conditions, their combined application makes it possible to decipher local-scale overprints from signals of past ocean oxygenation. It is therefore ideal, whenever possible, to measure both 98Mo and 205Tl in the same shale samples to assess past changes in ocean oxygenation.
Increasingly heavier 98Mo are found in shales deposited during the Neoarchean (2,800 to 2,500 million years ago, or Ma), which would be a predicted consequence of progressive ocean oxygenation across this timeframe. Increasingly heavier 205Tl across a well-documented Mesozoic Oceanic Anoxic Event (~94 Ma), on the other hand, would be a predicted consequence of progressive ocean de-oxygenation. An anti-correlation in the first combined application of Mo and Tl isotopes in ancient shales provides a strong fingerprint for previously unrecognized levels of ocean oxygenation at ~2,500 Ma. Lastly, neither 98Mo or 205Tl behave as predicted in shales deposited during three Ediacaran Ocean Oxygenation Events (~635 Ma, ~580 Ma, and ~560 Ma). These unexpected trends are due, at least in part, to local-scale overprints that must be taken into consideration when pairing together Mo and Tl isotopes in shales.
The ability of the Mo and Tl isotope systems to track changes in past ocean oxygenation is confirmed in this dissertation. Both isotope systems have the potential to track these changes independently, but their combined utility is particularly powerful. Under ideal conditions, their combined application can provide an even more robust fingerprint for changes in past ocean oxygenation. Even under non-ideal conditions, their combined application makes it possible to decipher local-scale overprints from signals of past ocean oxygenation. It is therefore ideal, whenever possible, to measure both 98Mo and 205Tl in the same shale samples to assess past changes in ocean oxygenation.
ContributorsOstrander, Chadlin Miles (Author) / Anbar, Ariel D (Thesis advisor) / Till, Christy B. (Committee member) / Wadhwa, Meenakshi (Committee member) / Hervig, Richard L (Committee member) / Mauskopf, Philip D (Committee member) / Arizona State University (Publisher)
Created2020