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Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding

Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding of the diagenetic processes that may affect molybdenum and uranium isotopes entering the rock record. Using samples from the Black Sea water column, the first water column profile of 238U/235U variations from a modern euxinic basin has been measured. This profile allows the direct determination of the 238U/235U fractionation factor in a euxinic marine setting. More importantly however, these data demonstrate the extent of Rayleigh fractionation of U isotopes that can occur in euxinic restricted basins. Because of this effect, the offset of 238U/235U between global average seawater and coeval black shales deposited in restricted basins is expected to depend on the degree of local uranium drawdown from the water column, potentially complicating the interpretation 238U/235U paleorecords. As an alternative to the black shales typically used for paleoredox reconstructions, molybdenum and uranium isotope variations in bulk carbonate sediments from the Bahamas are examined. The focus of this work was to determine what processes, if any, fractionate molybdenum and uranium isotopes during incorporation into bulk carbonate sediments and their subsequent diagenesis. The results demonstrate that authigenic accumulation of molybdenum and uranium from anoxic and sulfidic pore waters is a dominant process controlling the concentration and isotopic composition of these sediments during early diagenesis. Examination of ODP drill core samples from the Bahamas reveals similar behavior for sediments during the first ~780ka of burial, but provides important examples where isolated cores and samples occasionally demonstrate additional fractionation, the cause of which remains poorly understood.
ContributorsRomaniello, Stephen J. (Author) / Anbar, Ariel (Thesis advisor) / Hartnett, Hilairy (Committee member) / Herrmann, Achim (Committee member) / Shock, Everett (Committee member) / Wadhwa, Meenakshi (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Biochemical reactions underlie all living processes. Their complex web of interactions is difficult to fully capture and quantify with simple mathematical objects. Applying network science to biology has advanced our understanding of the metabolisms of individual organisms and the organization of ecosystems, but has scarcely been applied to life at

Biochemical reactions underlie all living processes. Their complex web of interactions is difficult to fully capture and quantify with simple mathematical objects. Applying network science to biology has advanced our understanding of the metabolisms of individual organisms and the organization of ecosystems, but has scarcely been applied to life at a planetary scale. To characterize planetary-scale biochemistry, I constructed biochemical networks using global databases of annotated genomes and metagenomes, and biochemical reactions. I uncover scaling laws governing biochemical diversity and network structure shared across levels of organization from individuals to ecosystems, to the biosphere as a whole. Comparing real biochemical reaction networks to random reaction networks reveals the observed biological scaling is not a product of chemistry alone, but instead emerges due to the particular structure of selected reactions commonly participating in living processes. I perform distinguishability tests across properties of individual and ecosystem-level biochemical networks to determine whether or not they share common structure, indicative of common generative mechanisms across levels. My results indicate there is no sharp transition in the organization of biochemistry across distinct levels of the biological hierarchy—a result that holds across different network projections.

Finally, I leverage these large biochemical datasets, in conjunction with planetary observations and computational tools, to provide a methodological foundation for the quantitative assessment of biology’s viability amongst other geospheres. Investigating a case study of alkaliphilic prokaryotes in the context of Enceladus, I find that the chemical compounds observed on Enceladus thus far would be insufficient to allow even these extremophiles to produce the compounds necessary to sustain a viable metabolism. The environmental precursors required by these organisms provides a reference for the compounds which should be prioritized for detection in future planetary exploration missions. The results of this framework have further consequences in the context of planetary protection, and hint that forward contamination may prove infeasible without meticulous intent. Taken together these results point to a deeper level of organization in biochemical networks than what has been understood so far, and suggests the existence of common organizing principles operating across different levels of biology and planetary chemistry.
ContributorsSmith, Harrison Brodsky (Author) / Walker, Sara I (Thesis advisor) / Anbar, Ariel D (Committee member) / Line, Michael R (Committee member) / Okie, Jordan G. (Committee member) / Romaniello, Stephen J. (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Characterizing the surface mineralogy of asteroids is critical to constraining their formation history and provides insight into the processes of planetary formation. One method of determining the surface mineralogy of asteroids is comparison of their visible to near-infrared reflectance (VNIR) spectra with laboratory spectra from meteorites and minerals. Subsequent in-situ

Characterizing the surface mineralogy of asteroids is critical to constraining their formation history and provides insight into the processes of planetary formation. One method of determining the surface mineralogy of asteroids is comparison of their visible to near-infrared reflectance (VNIR) spectra with laboratory spectra from meteorites and minerals. Subsequent in-situ investigation of these asteroids by spacecraft can supplement or supersede interpretations derived from Earth-based observations.I investigated a suite of aubrites, sulfide minerals, and metal-rich chondrites in a variety of forms (hand samples, powders, and slabs) to identify similarities with ‘spectrally featureless’ asteroids. I collected VNIR spectra and powder X-ray diffraction patterns of these samples and compared their overall reflectance and spectral slope with X-complex and T-, L-, and D-type asteroid spectra. The Psyche Mission will orbit asteroid (16) Psyche beginning in 2026. I provide a pre-flight assessment of the surface composition of Psyche by comparing spectra of Psyche to a large spectral library of possible surface analog materials (e.g., iron meteorites, mesosiderites, pallasites, sulfides, enstatite, ordinary, and metal-rich chondrites, endmember silicates, and mixtures of silicates, metal, and sulfides). Spectra of Psyche are generally consistent with iron meteorite powder, mixtures of iron meteorite powder and low-Fe, low-Ca pyroxene, sulfide minerals, and the CH/CBb chondrite Isheyevo. Next, I demonstrate some anticipated capabilities of the Psyche Multispectral Imager by comparing spectral parameters derived from Imager-convolved data to those from high resolution laboratory spectra. I offer preliminary strategies for classifying surface composition based on Imager filter ratios and overall reflectance. Last, I present an assessment of a benchtop, commercial-off-the-shelf (COTS) version of the Psyche Imager. The COTS Imager uses the same model CCD and a similar f-number commercial camera lens. I measured the gain, full well, linearity, read noise, quantum efficiency, and modulation transfer function to compare with eventual calibration data from the flight Imager. I validate the results of a radiometric model developed for the flight Imager with signal measurements from the COTS Imager. This work demonstrates that the COTS Imager is an effective testbed for validating Imager requirements and developing software and procedures for eventual calibration of the flight instrument.
ContributorsDibb, Steven (Author) / Bell, James (Thesis advisor) / Hardgrove, Craig (Committee member) / Garvie, Laurence (Committee member) / Elkins-Tanton, Linda (Committee member) / Bose, Maitrayee (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Space weathering of planetary surfaces is a complex process involving many mechanisms that work independently over different timescales. This research aims to address outstanding questions related to solar wind rim formation on space weathered regolith and tests a new hypothesis that dielectric breakdown plays an important role in the optical

Space weathering of planetary surfaces is a complex process involving many mechanisms that work independently over different timescales. This research aims to address outstanding questions related to solar wind rim formation on space weathered regolith and tests a new hypothesis that dielectric breakdown plays an important role in the optical maturation of lunar regolith. The purpose of this work is to highlight the limitations imposed by laboratory equipment to accurately simulate the solar wind’s effects on regolith and to provide physical context for the possible contributions of dielectric breakdown to space weathering. Terrestrial and lunar samples were experimentally irradiated and damage was characterized using electron microscopy techniques. Low-fluence proton irradiation produced differential weathering in a lunar mare basalt, with radiation damage on some phases being inconsistent with that found in the natural lunar environment. Dielectric breakdown of silicates revealed two electrical processes that produce characteristic surface and subsurface damage, in addition to amorphous rims. The results of this research highlight experimental parameters that if ignored, can significantly affect the results and interpretations of simulated solar wind weathering, and provides a framework for advancing space weathering research through experimental studies.
ContributorsShusterman, Morgan (Author) / Robinson, Mark S (Thesis advisor) / Sharp, Thomas G (Thesis advisor) / Hibbits, Charles (Committee member) / Bose, Maitrayee (Committee member) / Semken, Steven (Committee member) / Arizona State University (Publisher)
Created2023
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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

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.
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
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Description
The central question of my dissertation is "How old are the inner moons of Saturn?" This question is of critical importance for the refinement of how solar systems and giant planet systems form and evolve. One of the most direct ways to test the ages of a planet's surface is

The central question of my dissertation is "How old are the inner moons of Saturn?" This question is of critical importance for the refinement of how solar systems and giant planet systems form and evolve. One of the most direct ways to test the ages of a planet's surface is through the use of impact craters. Here I utilize images from the Cassini Imaging Science Subsystem (ISS) to count the craters on the mid-sized moons of Saturn, Tethys and Dione. I present a statistical analysis of the craters and the likely impactor sources that crated these craters. On Tethys I find that the impact craters can be explained by a planetocentric source that is local to the Saturnian system and is not found elsewhere in the outer planets. I also find that the majority of mapped regions are likely close in age. On Dione, I have mapped four areas at a regional-scale resolution ( ~ 200 m/ pix) and have found that resurfacing has greatly affected the small crater population and that the overall size-frequency distribution of craters is most representative of a planetocentric source unique to Saturn. Elliptical craters provide another means of assessing the bombardment environment around Saturn, as they record the primary direction of the object that created the crater upon impact on the surface. I have mapped these craters on Tethys and Dione, to analyze the global distributions of these craters and their orientations. Across both satellites, I find that in the equatorial regions between 30° N and 30°S in latitude, the orientations of the elliptical craters are consistent with an East/West orientation for their direction, which also is suggestive of a local planetocentric source. Throughout the main three studies presented in this dissertation I find that the main impactor source is a planetocentric source that is unique to Saturn and is not seen on the moons of the other giant planets.
ContributorsFerguson, Sierra Nichole (Author) / Rhoden, Alyssa R (Thesis advisor) / Desch, Steven J (Thesis advisor) / Robinson, Mark (Committee member) / Williams, David (Committee member) / Bose, Maitrayee (Committee member) / Arizona State University (Publisher)
Created2021