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- All Subjects: Geochemistry
- Creators: Sharp, Thomas
- Status: Published
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 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
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
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
The collision between the Indian and Eurasian tectonic plates marked the onset of the rise of the Himalayan-Tibetan orogen, but also brought about profound changes to the Earth's oceans and climate. The exact sequence of events that occurred during this collision is poorly understood, leading to a wide range of estimates of its age. The Indus and Yarlung sutures are generally considered to represent the final collision between India and Eurasia, and together form a mostly continuous belt that can be traced over 2000 km along strike. In the western portions of the orogen the Karakoram Fault introduces a key complexity to the study of timing of collision by offsetting the Indus and Yarlung sutures. Recent work has used the complexities introduced by the Karakoram Fault to suggest that the more northerly Shyok suture, not the Indus suture, represents the India-Eurasia collision zone. Estimates for timing of the India-Eurasia collision fall into one of three groups: 40-34 Ma, 55-50 Ma, and 66-60 Ma. Attempts to reconcile these models have thus far been unsuccessful. In order to provide additional data that might further clarify the timing and location of collision, studies have been performed along the Shyok suture in India and along the Yarlung suture in Tibet at Sangsang. A study along the Shyok suture argues that the suture formed between 92-85 Ma. This timing precludes an interpretation that the Shyok suture marks the location of the India-Eurasia collision. A second study demonstrates the utility of two new geochronometers, (U-Th)/Pb joaquinite and 40Ar/39Ar neptunite, that play an important role in unraveling the tectonic history of the Yarlung suture. A third study is an investigation of the structure and geochronology of the Sangsang ophiolite complex. Here, multiple (U-Th)/Pb and 40Ar/39Ar systems record magmatism and metamorphism spanning ca. 125-52 Ma. By tying these chronometers to tectonic process, a history is reconstructed of the southern margin of Tibet that includes Early Cretaceous to Late Cretaceous forearc rifting associated with mid ocean ridge subduction, Paleocene accretionary wedge uplift and erosion, and finally Eocene metasomatism and collision.
ContributorsBorneman, Nathaniel (Author) / Hodges, Kip (Thesis advisor) / Reynolds, Stephen (Committee member) / Whipple, Kelin (Committee member) / Sharp, Thomas (Committee member) / Tyburczy, James (Committee member) / Arizona State University (Publisher)
Created2016
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
Chemical and physical interactions of flowing ice and rock have inexorably shaped planetary surfaces. Weathering in glacial environments is a significant link in biogeochemical cycles – carbon and strontium – on Earth, and may have once played an important role in altering Mars’ surface. Despite growing recognition of the importance of low-temperature chemical weathering, these processes are still not well understood. Debris-coated glaciers are also present on Mars, emphasizing the need to study ice-related processes in the evolution of planetary surfaces. During Earth’s history, subglacial environments are thought to have sheltered communities of microorganisms from extreme climate variations. On Amazonian Mars, glaciers such as lobate debris aprons (LDA) could have hosted chemolithotrophic communities, making Mars’ present glaciers candidates for life preservation. This study characterizes glacial processes on both Earth and Mars.
Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.
Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.
I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.
Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.
I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
ContributorsRutledge, Alicia Marie (Author) / Christensen, Philip R. (Thesis advisor) / Shock, Everett (Committee member) / Clarke, Amanda (Committee member) / Sharp, Thomas (Committee member) / Whipple, Kelin (Committee member) / Arizona State University (Publisher)
Created2015
Description
Archean oxidative weathering reactions were likely important O2 sinks that delayed the oxygenation of Earth’s atmosphere, as well as sources of bio-essential trace metals such as Mo to the biosphere. However, the rates of these reactions are difficult to quantify experimentally at relevantly low concentrations of O2. With newly developed O2 sensors, weathering experiments were conducted to measure the rate of sulfide oxidation at Archean levels of O2, a level three orders of magnitude lower than previous experiments. The rate laws produced, combined with weathering models, indicate that crustal sulfide oxidation by O2 was possible even in a low O2 Archean atmosphere.
Given the experimental results, it is expected that crustal delivery of bio-essential trace metals (such as Mo) from sulfide weathering was active even prior to the oxygenation of Earth’s atmosphere. Mo is a key metal for biological N2 fixation and its ancient use is evidenced by N isotopes in ancient sedimentary rocks. However, it is typically thought that Mo was too low to be effectively bioavailable early in Earth’s history, given the low abundances of Mo found in ancient sediments. To reconcile these observations, a computational model was built that leverages isotopic constraints to calculate the range of seawater concentrations possible in ancient oceans. Under several scenarios, bioavailable concentrations of seawater Mo were attainable and compatible with the geologic record. These results imply that Mo may not have been limiting for early metabolisms.
Titanium (Ti) isotopes were recently proposed to trace the evolution of the ancient continental crust, and have the potential to trace the distribution of other trace metals during magmatic differentiation. However, significant work remains to understand fully Ti isotope fractionation during crust formation. To calibrate this proxy, I carried out the first direct measurement of mineral-melt fractionation factors for Ti isotopes in Kilauea Iki lava lake and built a multi-variate fractionation law for Ti isotopes during magmatic differentiation. This study allows more accurate forward-modeling of isotope fractionation during crust differentiation, which can now be paired with weathering models and ocean mass balance to further reconstruct the composition of Earth’s early continental crust, atmosphere, and oceans.
Given the experimental results, it is expected that crustal delivery of bio-essential trace metals (such as Mo) from sulfide weathering was active even prior to the oxygenation of Earth’s atmosphere. Mo is a key metal for biological N2 fixation and its ancient use is evidenced by N isotopes in ancient sedimentary rocks. However, it is typically thought that Mo was too low to be effectively bioavailable early in Earth’s history, given the low abundances of Mo found in ancient sediments. To reconcile these observations, a computational model was built that leverages isotopic constraints to calculate the range of seawater concentrations possible in ancient oceans. Under several scenarios, bioavailable concentrations of seawater Mo were attainable and compatible with the geologic record. These results imply that Mo may not have been limiting for early metabolisms.
Titanium (Ti) isotopes were recently proposed to trace the evolution of the ancient continental crust, and have the potential to trace the distribution of other trace metals during magmatic differentiation. However, significant work remains to understand fully Ti isotope fractionation during crust formation. To calibrate this proxy, I carried out the first direct measurement of mineral-melt fractionation factors for Ti isotopes in Kilauea Iki lava lake and built a multi-variate fractionation law for Ti isotopes during magmatic differentiation. This study allows more accurate forward-modeling of isotope fractionation during crust differentiation, which can now be paired with weathering models and ocean mass balance to further reconstruct the composition of Earth’s early continental crust, atmosphere, and oceans.
ContributorsJohnson, Aleisha (Author) / Anbar, Ariel D. (Thesis advisor) / Till, Christy (Committee member) / Hartnett, Hilairy (Committee member) / Romaniello, Stephen J. (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2020