Matching Items (56)
Description
Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to petroleum generation and to chemoautotrophic microbial communities. There have been numerous studies on the reactivity of organic compounds in water at elevated temperatures, but these studies rarely explore the consequences of inorganic solutes in hydrothermal fluids. The experiments in this thesis explore new reaction pathways of organic compounds mediated by aqueous and solid phase metals, mainly Earth-abundant copper. These experiments show that copper species have the potential to oxidize benzene and toluene, which are typically viewed as unreactive. These pathways add to the growing list of known organic transformations that are possible in natural hydrothermal systems. In addition to the characterization of reactions in natural systems, there has been recent interest in using hydrothermal conditions to facilitate organic transformations that would be useful in an applied, industrial or synthetic setting. This thesis identifies two sets of conditions that may serve as alternatives to commonplace industrial processes. The first process is the oxidation of benzene with copper to form phenol and chlorobenzene. The second is the copper mediated dehalogenation of aryl halides. Both of these processes apply the concepts of geomimicry by carrying out organic reactions under Earth-like conditions. Only water and copper are needed to implement these processes and there is no need for exotic catalysts or toxic reagents.
ContributorsLoescher, Grant (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Gould, Ian (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
Description
Astrobiology is premised on the idea that life beyond Earth can exist. Yet, everything known about life is derivative from life on Earth. To understand life beyond Earth, then, requires a definition of life that is abstracted beyond a particular geophysical context. To do this requires a formal understanding of the physical mechanisms by which matter is animated into life. At current, such descriptions are completely lacking for the emergence of life, but do exist for the emergence of consciousness. Namely, contemporary neuroscience offers definitions for universal physical processes that are in one-to-one correspondence with conscious experience. Since consciousness is a sufficient condition for life, these universal definitions of consciousness offer an interesting way forward in terms of the search for life in the cosmos. In this work, I systematically examine Integrated Information Theory (IIT), a well-established theory of consciousness, with the aim of applying it in both biological and astrobiological settings. Surprisingly, I discover major problems with Integrated Information Theory on two fronts: mathematical and epistemological. On the mathematical side, I show how degeneracies buried deep within the theory render it mathematically ill-defined, while on the epistemological side, I prove that the postulates of IIT are scientifically unfalsifiable and inherently metaphysical. Given that IIT is the preeminent theory of consciousness in modern neuroscience, these results have far-reaching implications in this field. In addition, I show that the epistemic issues of falsifiability that hamstring IIT apply quite generally to all contemporary theories of consciousness, which suggests a major reframing of the problem is necessary. The problems that I reveal in regard to defining consciousness offer an important parallel in regard to defining life, as both fields seek to define their topic of study in absence of an existing theoretical framework. To avoid metaphysical problems related to falsifiability, universal theories of both life and consciousness must be framed with respect to independent empirical observations that can be used to benchmark predictions from the theory. In this regard, I argue that the epistemic debate over scientific theories of consciousness should be used to inform the discussion regarding theoretical definitions of life.
ContributorsHanson, Jake (Author) / Walker, Sara I (Thesis advisor) / Desch, Steven J (Committee member) / Pavlic, Theodore P (Committee member) / Groppi, Christopher E (Committee member) / Shim, Sang-Heon (Committee member) / Arizona State University (Publisher)
Created2021
Description
A novel technique for measuring heavy trace elements in geologic materials with secondary ion mass spectrometry (SIMS) is presented. This technique combines moderate levels of mass resolving power (MRP) with energy filtering in order to remove molecular ion interferences while maintaining enough sensitivity to measure trace elements. The technique was evaluated by measuring a set of heavy chalcophilic elements in two sets of doped glasses similar in composition to rhyolites and basalts, respectively. The normalized count rates of Cu, As, Se, Br, and Te were plotted against concentrations to test that the signal increased linearly with concentration. The signal from any residual molecular ion interferences (e.g. ²⁹Si³⁰Si¹⁶O on ⁷⁵As) represented apparent concentrations ≤ 1 μg/g for most of the chalcophiles in rhyolitic matrices and between 1 and 10 μg/g in basaltic compositions. This technique was then applied to two suites of melt inclusions from the Bandelier Tuff: Ti-rich, primitive and Ti-poor, evolved rhyolitic compositions. The results showed that Ti-rich inclusions contained ~30 μg/g Cu and ~3 μg/g As while the Ti-poor inclusions contained near background Cu and ~6 μg/g As. Additionally, two of the Ti-rich inclusions contained > 5 μg/g of Sb and Te, well above background. Other elements were at or near background. This suggests certain chalcophilic elements may be helpful in unraveling processes relating to diversity of magma sources in large eruptions. Additionally, an unrelated experiment is presented demonstrating changes in the matrix effect on SIMS counts when normalizing against ³⁰Si⁺ versus ²⁸Si²⁺. If one uses doubly charged silicon as a reference, (common when using large-geometry SIMS instruments to study the light elements Li - C) it is important that the standards closely match the major element chemistry of the unknown.
ContributorsCarlson, Eric Norton (Author) / Hervig, Richard L (Thesis advisor) / Roggensack, Kurt (Committee member) / Burt, Donald M (Committee member) / Arizona State University (Publisher)
Created2021
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 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
Description
Dissolved organic matter (DOM) can have numerous effects on the water chemistry and the biological life within an aquatic system with its wide variety of chemical structures and properties. The composition of the dissolved carbon can be estimated by utilizing the fluorescent properties of some DOM such as aromatic amino acids and humic material. This experiment was used to observe how organic matter could influence hydrothermal systems, such as Sylvan Springs in Yellowstone National Park, USA. Using optical density at 600 nm (OD 600), excitation-emission matrix spectra (EEMS), and Illumina sequencing methods (16S rRNA gene sequencing), changes in dissolved organic matter (DOM) were observed based on long term incubation at 84ºC and microbial influence. Four media conditions were tested over a two-month duration to assess these changes: inoculated pine needle media, uninoculated pine needle media, inoculated yeast extract media, and uninoculated yeast extract media. The inoculated samples contained microbes from a fluid and sediment sample of Sylvan Spring collected July 23, 2018. Absorbance indicated that media containing pine needle broth poorly support life, whereas media containing yeast extract revealed a positive increase in growth. Excitation-Emission Matrix Spectra of the all media conditions indicated changes in DOM composition throughout the trial. There were limited differences between the inoculated and uninoculated samples suggesting that the DOM composition change in this study was dominated by the two-month incubation at 84ºC more than biotic processes. Sequencing performed on a sediment sample collected from Sylvan Spring indicated five main order of prokaryotic phyla: Aquificales, Desulfurococcales, Thermoproteales, Thermodesulfobacteriales, and Crenarchaeota. These organisms are not regarded as heterotrophic microbes, so the lack of significant biotic changes in DOM could be a result of these microorganisms not being able to utilize these enrichments as their main metabolic energy supply.
ContributorsKnott, Nicholas Joseph (Author) / Shock, Everett (Thesis director) / Hartnett, Hilairy (Committee member) / Till, Christy (Committee member) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
Freshwater ecosystems are increasingly threatened by anthropogenic eutrophication (Kolzau et al., 2014) and require mitigation efforts to prevent oxygen depletion and subsequent biodiversity loss. Tres Rios Constructed Treatment Wetland (CTW) relies on wetland ecosystem functioning to reduce nutrient concentrations in order to meet regulatory guidelines. I investigated the impact of solar irradiance, temperature, and nutrient availability on aquatic net primary productivity, ecosystem respiration, and nutrient cycling using statistical analysis and quantitative modeling informed by field data generated by ASU’s Wetland Ecosystem Ecology Lab (WEEL) in partnership with the City of Phoenix Water Services Department. I found that the extent of daily solar insolation controls Aquatic Net Primary Productivity (ANPP) rates and the seasonal aquatic nutrient processing capacity of Tres Rios, resulting in the following approximate relationship: ANPP = 0.001344(W/m²) - 0.32634 (r² = 0.259; p = 0.005).
This formula was used to estimate the nutrient uptake performance of aquatic primary producers from sampling observations; ANPP accounted for 16.26 metric tons of system wide N uptake, while aquatic ER contributed 6.07 metric tons N of nighttime remineralization and 5.7 metric tons of N throughout the water column during the day. The estimated yearly net aquatic N flux is 4.49 metric tons uptake, compared to about 12 metric tons yearly N uptake by the vegetated marsh (Treese, 2019). However, not accounting for animal respiration results in an underestimation of system-wide N remineralization, and not accounting for soil processes results in an underestimation of N uptake.
This formula was used to estimate the nutrient uptake performance of aquatic primary producers from sampling observations; ANPP accounted for 16.26 metric tons of system wide N uptake, while aquatic ER contributed 6.07 metric tons N of nighttime remineralization and 5.7 metric tons of N throughout the water column during the day. The estimated yearly net aquatic N flux is 4.49 metric tons uptake, compared to about 12 metric tons yearly N uptake by the vegetated marsh (Treese, 2019). However, not accounting for animal respiration results in an underestimation of system-wide N remineralization, and not accounting for soil processes results in an underestimation of N uptake.
ContributorsEvans, Joseph Barrett (Author) / Childers, Daniel (Thesis director) / Hartnett, Hilairy (Committee member) / Watts College of Public Service & Community Solut (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
Tempe Town Lake is the site of fifteen years’ worth of chemical data collection by ASU researchers. In 2018 the dataSONDE, an instrument capable of measuring different water quality parameters every thirty minutes for a month at a time was installed in the lake. The SONDE has the potential to completely reduce the need for sampling by hand. Before the SONDE becomes the sole means of gathering data, it is important to verify its accuracy. In this study, the measurements gathered by the SONDE (pH, dissolved oxygen, temperature, conductivity and colored dissolved organic matter) were compared to measurements gathered using the verified methods from the past fifteen years.
ContributorsSauer, Elinor Rayne (Author) / Hartnett, Hilairy (Thesis director) / Glaser, Donald (Committee member) / Shock, Everett (Committee member) / Historical, Philosophical & Religious Studies (Contributor) / School of Molecular Sciences (Contributor) / School of Life Sciences (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2020-12
Description
Dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) are crucial nutrients for autotrophic and heterotrophic microbial life, respectively, in hydrothermal systems. Biogeochemical processes that control amounts of DIC and DOC in Yellowstone hot springs can be investigated by measuring carbon abundances and respective isotopic values. A decade and a half of field work in 10 regions within Yellowstone National Park and subsequent geochemical lab analyses reveal that sulfate-dominant acidic regions have high DOC (Up to 57 ppm C) and lower DIC (up to 50 ppm C) compared to neutral-chloride regions with low DOC (< 2 ppm C) and higher DIC (up to 100 ppm C). Abundances and isotopic data suggest that sedimentary rock erosion by acidic hydrothermal fluids, fresh snow-derived meteoric water, and exogenous carbon input allowed by local topography may affect DOC levels. Evaluating the isotopic compositions of DIC and DOC in hydrothermal fluids gives insight on the geology and microbial life in the subsurface between different regions. DIC δ13C values range from -4‰ to +5‰ at pH 5-9 and from -10‰ to +3‰ at pH 2-5 with several springs lower than -10‰. DOC δ13C values parkwide range from -10‰ to -30‰. Within this range, neutral-chloride regions in the Lower Geyser Basin have lighter isotopes than sulfate-dominant acidic regions. In hot springs with elevated levels of DOC, the range only varies between -20‰ and -26‰ which may be caused by local exogenous organic matter runoff. Combining other geochemical measurements, such as differences in chloride and sulfate concentrations, demonstrates that some regions contain mixtures of multiple fluids moving through the complex hydrological system in the subsurface. The mixing of these fluids may account for increased levels of DOC in meteoric sulfate-dominant acidic regions. Ultimately, the foundational values of dissolved carbon and their isotopic composition is provided in a parkwide study, so results can be combined with future studies that apply different sequencing analyses to understand specific biogeochemical cycling and microbial communities that occur in individual hot springs.
ContributorsBarnes, Tanner (Author) / Shock, Everett (Thesis advisor) / Meyer-Dombard, D'Arcy (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2023
Iron Cycling May Lower Methane Fluxes at an Impounded Marsh: Evidence from the Herring River Estuary
Description
Wetlands produce approximately one third of total global methane emissions and sequester significant amounts of CO2. Salt marshes make up 5% of total wetland area, and therefore are key factors affecting global methane and CO2 emissions. Many marshes are anthropogenically managed either by diking, draining, impoundment, or otherwise restricting tidal exchange. This causes marsh freshening, increases methane emissions, and releases sequestered carbon, all of which can lead to a warming effect on the climate by the greenhouse effect. We studied the formerly impounded Old County salt marsh, found in the Herring River Estuary of Wellfleet, Massachusetts, USA. The USGS Woods Hole Coastal and Marine Science Center installed two eddy covariance flux towers in the Herring River Estuary. These showed that Old County had low methane fluxes (17 nmol/m2/s) compared to another site in the same estuary (112 nmol/m2/s). The question became; why did Old County experience lower methane emissions? We then did a focused study on the Old County location to investigate. We sampled various biogeochemical parameters including pH, salinity, ORP, dissolved Fe, sulfate, chloride, CH4, DOC, and DIC from pore water samples taken June 2022. We also measured extractable iron from a 2015 archived sediment core at Old County. Specifically, we explored the role of Fe in reducing methane through Fe coupled anaerobic oxidation of methane (Fe-AOM). The porewater depth profiles ranged from 10cm to 242 cm in depth and showed Old County as acidic (pH of 3-6.5), mostly fresh, anoxic, highly reducing, and high in dissolved organic carbon (DOC; 2,000-10,000 μM). I divided the depth profiles into two distinct zones, one above 50 cm and one below 50 cm. Overall, Fe-AOM was likely to occur below 50 cm because dissolved Fe increased as CH4 decreased, which is the expected pattern for Fe-AOM. Also, because the ratio of the calculated methane flux (-0.552 nmol m-2 s-1) to the dissolved Fe (0.072 nmol m-2 s-1) was 7.6, which closely matched the 1 to 8 stoichiometry of the Fe-AOM reactions.
ContributorsEinecker, Rachel (Author) / Hartnett, Hilairy (Thesis director) / Anbar, Ariel (Committee member) / Eagle, Meagan (Committee member) / Barrett, The Honors College (Contributor) / School of Molecular Sciences (Contributor)
Created2023-12