Matching Items (8)
Filtering by

Clear all filters

151140-Thumbnail Image.png
Description
Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding

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
156916-Thumbnail Image.png
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
153685-Thumbnail Image.png
Description
Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the

Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the mantle) is less so. In fact, the hydrogen isotope composition of the primordial martian mantle is of great interest since it has implications for the origin and abundance of water on that planet. Martian meteorites could provide key constraints in this regard, since they crystallized from melts originating from the martian mantle and contain phases that potentially record the evolution of the H2O content and isotopic composition of the interior of the planet over time. Examined here are the hydrogen isotopic compositions of Nominally Anhydrous Phases (NAPs) in eight martian meteorites (five shergottites and three nakhlites) using Secondary Ion Mass Spectrometry (SIMS).

This study presents a total of 113 individual analyses of H2O contents and hydrogen isotopic compositions of NAPs in the shergottites Zagami, Los Angeles, QUE 94201, SaU 005, and Tissint, and the nakhlites Nakhla, Lafayette, and Yamato 000593. The hydrogen isotopic variation between and within meteorites may be due to one or more processes including: interaction with the martian atmosphere, magmatic degassing, subsolidus alteration (including shock), and/or terrestrial contamination. Taking into consideration the effects of these processes, the hydrogen isotope composition of the martian mantle may be similar to that of the Earth. Additionally, this study calculated upper limits on the H2O contents of the shergottite and nakhlite parent melts based on the measured minimum H2O abundances in their maskelynites and pyroxenes, respectively. These calculations, along with some petrogenetic assumptions based on previous studies, were subsequently used to infer the H2O contents of the mantle source reservoirs of the depleted shergottites (200-700 ppm) and the nakhlites (10-100 ppm). This suggests that mantle source of the nakhlites is systematically drier than that of the depleted shergottites, and the upper mantle of Mars may have preserved significant heterogeneity in its H2O content. Additionally, this range of H2O contents is not dissimilar to the range observed for the Earth’s upper mantle.
ContributorsTucker, Kera (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Till, Christy (Committee member) / Arizona State University (Publisher)
Created2015
154970-Thumbnail Image.png
Description
Shock metamorphism in meteorites constrains the impact histories of asteroids and planets. Shock-induced high-pressure (HP) minerals can provide more precise estimates of shock conditions than shock-induced deformation effects. In this research, I use shock features, particularly HP minerals, in ordinary-chondrite samples to constrain not only shock pressures but also the

Shock metamorphism in meteorites constrains the impact histories of asteroids and planets. Shock-induced high-pressure (HP) minerals can provide more precise estimates of shock conditions than shock-induced deformation effects. In this research, I use shock features, particularly HP minerals, in ordinary-chondrite samples to constrain not only shock pressures but also the pressure-temperature-time (P-T-t) paths they experienced.

Highly shocked L5/6 chondrites Acfer 040, Mbale, NWA 091 and Chico and LL6 chondrite NWA 757 were used to investigate a variety of shock pressures and post-shock annealing histories. NWA 757 is the only highly shocked LL chondrite that includes abundant HP minerals. The assemblage of ringwoodite and majoritic garnet indicates an equilibration shock pressure of ~20 GPa, similar to many strongly shocked L chondrites. Acfer 040 is one of the only two chondrite samples with bridgmanite (silicate perovskite), suggesting equilibration pressure >25 GPa. The bridgmanite, which is unstable at low-pressure, was mostly vitrified during post-shock cooling. Mbale demonstrates an example of elevated post-shock temperature resulting in back-transformation of ringwoodite to olivine. In contrast, majoritic garnet in Mbale survives as unambiguous evidence of strong shock. In these two samples, HP minerals are exclusively associated with shock melt, indicating that elevated shock temperatures are required for rapid mineral transformations during the transient shock pulse. However, elevated post-shock temperatures can destroy HP minerals: in temperature sequence from bridgmanite to ringwoodite then garnet. NWA 091 and Chico are impact melt breccias with pervasive melting, blackening of silicates, recrystallization of host rock but no HP minerals. These features indicate near whole-rock-melting conditions. However, the elevated post-shock temperatures of these samples has annealed out HP signatures. The observed shock features result from a complex P-T-t path and may not directly reflect the peak shock pressure. Although HP minerals provide robust evidence of high pressure, their occurrence also requires high shock temperatures and rapid cooling during the shock pulse. The most highly shocked samples lack HP signatures but have abundant high-temperature features formed after pressure release.
ContributorsHu, Jinping (Author) / Sharp, Thomas G. (Thesis advisor) / Tyburczy, James A. (Committee member) / Leinenweber, Kurt (Committee member) / Wadhwa, Meenakshi (Committee member) / Zolotov, Mikhail (Committee member) / Arizona State University (Publisher)
Created2016
155860-Thumbnail Image.png
Description
Impact cratering has played a key role in the evolution of the solid surfaces of Solar System bodies. While much of Earth’s impact record has been erased, its Moon preserves an extensive history of bombardment. Quantifying the timing of lunar impact events is crucial to understanding how impacts have shaped

Impact cratering has played a key role in the evolution of the solid surfaces of Solar System bodies. While much of Earth’s impact record has been erased, its Moon preserves an extensive history of bombardment. Quantifying the timing of lunar impact events is crucial to understanding how impacts have shaped the evolution of early Earth, and provides the basis for estimating the ages of other cratered surfaces in the Solar System.

Many lunar impact melt rocks are complex mixtures of glassy and crystalline “melt” materials and inherited clasts of pre-impact minerals and rocks. If analyzed in bulk, these samples can yield complicated incremental release 40Ar/39Ar spectra, making it challenging to uniquely interpret impact ages. Here, I have used a combination of high-spatial resolution 40Ar/39Ar geochronology and thermal-kinetic modeling to gain new insights into the impact histories recorded by such lunar samples.

To compare my data to those of previous studies, I developed a software tool to account for differences in the decay, isotopic, and monitor age parameters used for different published 40Ar/39Ar datasets. Using an ultraviolet laser ablation microprobe (UVLAMP) system I selectively dated melt and clast components of impact melt rocks collected during the Apollo 16 and 17 missions. UVLAMP 40Ar/39Ar data for samples 77135, 60315, 61015, and 63355 show evidence of open-system behavior, and provide new insights into how to interpret some complexities of published incremental heating 40Ar/39Ar spectra. Samples 77115, 63525, 63549, and 65015 have relatively simple thermal histories, and UVLAMP 40Ar/39Ar data for the melt components of these rocks indicate the timing of impact events—spanning hundreds of millions of years—that influenced the Apollo 16 and 17 sites. My modeling and UVLAMP 40Ar/39Ar data for sample 73217 indicate that some impact melt rocks can quantitatively retain evidence for multiple melt-producing impact events, and imply that such polygenetic rocks should be regarded as high-value sampling opportunities during future exploration missions to cratered planetary surfaces. Collectively, my results complement previous incremental heating 40Ar/39Ar studies, and support interpretations that the Moon experienced a prolonged period of heavy bombardment early in its history.
ContributorsMercer, Cameron Mark (Author) / Hodges, Kip V (Thesis advisor) / Robinson, Mark S (Committee member) / Wadhwa, Meenakshi (Committee member) / Desch, Steven J (Committee member) / Hervig, Richard L (Committee member) / Arizona State University (Publisher)
Created2017
158384-Thumbnail Image.png
Description
This study explores how bulk composition and oxygen fugacity (fO2) affect the partitioning of sulfur between the molten mantle and core of an early planetesimal. The model can be used to determine the range of potential sulfur concentrations in the asteroid (16) Psyche, which is the target of the National

This study explores how bulk composition and oxygen fugacity (fO2) affect the partitioning of sulfur between the molten mantle and core of an early planetesimal. The model can be used to determine the range of potential sulfur concentrations in the asteroid (16) Psyche, which is the target of the National Aeronautics and Space Administration/Arizona State University Psyche Mission. This mission will be our visit to an M-type asteroid, thought to be dominantly metallic.

The model looks at how oxygen fugacity (fO2), bulk composition, temperature, and pressure affect sulfur partitioning in planetesimals using experimentally derived equations from previous studies. In this model, the bulk chemistry and oxygen fugacity of the parent body is controlled by changing the starting material, using ordinary chondrites (H, L, LL) and carbonaceous chondrites (CM, CI, CO, CK, CV). The temperature of the planetesimal is changed from 1523 K to 1873 K, the silicate mobilization and total melting temperatures, respectively; and pressure from 0.1 to 20 GPa, the core mantle boundary pressures of Vesta and Mars, respectively.

The final sulfur content of a differentiated planetesimal core is strongly dependent on the bulk composition of the original parent body. In all modeled cores, the sulfur content is above 5 weight percent sulfur; this is the point at which the least amount of other light elements is needed to form an immiscible sulfide liquid in a molten core. Early planetesimal cores likely formed an immiscible sulfide liquid, a eutectic sulfide liquid, or potentially were composed of mostly troilite, FeS.
ContributorsBercovici, Hannah La'ia (Author) / Elkins-Tanton, Linda T. (Thesis advisor) / Garvie, Laurence (Committee member) / Wadhwa, Meenakshi (Committee member) / Arizona State University (Publisher)
Created2020
158429-Thumbnail Image.png
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
158231-Thumbnail Image.png
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

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.
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