Matching Items (50)
Description
Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so the unambiguous identification of these phases is important for understanding the geologic history of Mars. Secondary amorphous silicates are poorly understood and underrepresented in spectral libraries because they lack the long-range structural order that makes their crystalline counterparts identifiable in most analytical techniques. Fortunately, even amorphous materials have some degree of short-range order so that distinctions can be made with careful characterization.
Two sets of laboratory experiments were used to produce and characterize amorphous weathering products under probable conditions for the Martian surface, and one global spectral analysis using thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) instrument was used to constrain variations in amorphous silicates across the Martian surface. The first set of experiments altered crystalline and glassy basalt samples in an open system under strong (pH 1) and moderate (pH 3) acidic conditions. The second set of experiments simulated a current-day Martian weathering scenario involving transient liquid water where basalt glass weathering solutions, formed in circumneutral (pH ~5.5 and 7) conditions, were rapidly evaporated, precipitating amorphous silicates. The samples were characterized using visible and near-infrared (VNIR) spectroscopy, TIR spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD).
All experiments formed amorphous silicate phases that are new to spectral libraries. Moderately acidic alteration experiments produced no visible or spectral evidence of alteration products, whereas exposure of basalt glass to strongly acidic fluids produced silica-rich alteration layers that are spectrally consistent with VNIR and TIR spectra from the circum-polar region of Mars, indicating this region has undergone acidic weathering. Circum-netural pH basalt weathering solution precipitates are consistent with amorphous materials measured by rovers in soil and rock surface samples in Gale and Gusev Craters, suggesting transient water interactions over the last 3 billion years. Global spectral analyses determine that alteration conditions have varied across the Martian surface, and that alteration has been long lasting.
Two sets of laboratory experiments were used to produce and characterize amorphous weathering products under probable conditions for the Martian surface, and one global spectral analysis using thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) instrument was used to constrain variations in amorphous silicates across the Martian surface. The first set of experiments altered crystalline and glassy basalt samples in an open system under strong (pH 1) and moderate (pH 3) acidic conditions. The second set of experiments simulated a current-day Martian weathering scenario involving transient liquid water where basalt glass weathering solutions, formed in circumneutral (pH ~5.5 and 7) conditions, were rapidly evaporated, precipitating amorphous silicates. The samples were characterized using visible and near-infrared (VNIR) spectroscopy, TIR spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD).
All experiments formed amorphous silicate phases that are new to spectral libraries. Moderately acidic alteration experiments produced no visible or spectral evidence of alteration products, whereas exposure of basalt glass to strongly acidic fluids produced silica-rich alteration layers that are spectrally consistent with VNIR and TIR spectra from the circum-polar region of Mars, indicating this region has undergone acidic weathering. Circum-netural pH basalt weathering solution precipitates are consistent with amorphous materials measured by rovers in soil and rock surface samples in Gale and Gusev Craters, suggesting transient water interactions over the last 3 billion years. Global spectral analyses determine that alteration conditions have varied across the Martian surface, and that alteration has been long lasting.
ContributorsSmith, Rebecca (Author) / Christensen, Philip R. (Philip Russel) (Thesis advisor) / Shock, Everett (Committee member) / Hartnett, Hilairy (Committee member) / Shim, Sang-Heon (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2016
Description
One goal of geobiochemistry is to follow geochemical energy supplies from the external environment to the inside of microbial cells. This can be accomplished by combining thermodynamic calculations of energy supplies from geochemical processes and energy demands for biochemical processes. Progress towards this goal is summarized here. A critique of all thermodynamic data for biochemical compounds involved in the citric acid cycle (CAC) and the formulation of metabolite properties allows predictions of the energy involved in each step of the cycle as well as the full forward and reverse cycles over wide ranges of temperature and pressure. These results allow evaluation of energy demands at the center of many microbial metabolic systems. Field work, sampling, and lab analyses from two low-temperature systems, a serpentinizing system, and a subglacial setting, provide the data used in these thermodynamic analyses of energy supplies. An extensive literature summary of microbial and molecular data from serpentinizing systems found is used to guide the evaluation and ranking of energy supplies used by chemolithoautotrophic microbes. These results constrain models of the distribution of microbial metabolisms throughout the low-temperature serpentinization systems in the Samail ophiolite in Oman (including locales of primary and subsequent alteration processes). Data collected from Robertson Glacier in Alberta, Canada, together with literature data from Lake Vida in Antarctica and bottom seawater, allowed thermodynamic analyses of low-temperature energy supplies in a glacial system. Results for 1460 inorganic redox reactions are used to fully inventory the geochemical energy sources that support the globally extensive cold biosphere.
ContributorsCanovas, Peter Anthony (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Sharp, Thomas (Committee member) / Tyburczy, James (Committee member) / Heimsath, Arjun (Committee member) / Arizona State University (Publisher)
Created2016
Description
Applications of non-traditional stable isotope variations are moving beyond geosciences to biomedicine, made possible by advances in multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) technology. Mass-dependent isotope variation can provide information about the sources of elements and the chemical reactions that they undergo. Iron and calcium isotope systematics in biomedicine are relatively unexplored but have great potential scientific interest due to their essential nature in metabolism. Iron, a crucial element in biology, fractionates during biochemically relevant reactions. To test the extent of this fractionation in an important reaction process, equilibrium iron isotope fractionation during organic ligand exchange was determined. The results show that iron fractionates during organic ligand exchange, and that isotope enrichment increases as a function of the difference in binding constants between ligands. Additionally, to create a mass balance model for iron in a whole organism, iron isotope compositions in a whole mouse and in individual mouse organs were measured. The results indicate that fractionation occurs during transfer between individual organs, and that the whole organism was isotopically light compared with food. These two experiments advance our ability to interpret stable iron isotopes in biomedicine. Previous research demonstrated that calcium isotope variations in urine can be used as an indicator of changes in net bone mineral balance. In order to measure calcium isotopes by MC-ICP-MS, a chemical purification method was developed to quantitatively separate calcium from other elements in a biological matrix. Subsequently, this method was used to evaluate if calcium isotopes respond when organisms are subjected to conditions known to induce bone loss: 1) Rhesus monkeys were given an estrogen-suppressing drug; 2) Human patients underwent extended bed rest. In both studies, there were rapid, detectable changes in calcium isotope compositions from baseline - verifying that calcium isotopes can be used to rapidly detect changes in bone mineral balance. By characterizing iron isotope fractionation in biologically relevant processes and by demonstrating that calcium isotopes vary rapidly in response to bone loss, this thesis represents an important step in utilizing these isotope systems as a diagnostic and mechanistic tool to study the metabolism of these elements in vivo.
ContributorsMorgan, Jennifer Lynn Louden (Author) / Anbar, Ariel D. (Thesis advisor) / Wasylenki, Laura E. (Committee member) / Jones, Anne K. (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2011
Description
In oxygenic photosynthesis, Photosystem I (PSI) and Photosystem II (PSII) are two transmembrane protein complexes that catalyze the main step of energy conversion; the light induced charge separation that drives an electron transfer reaction across the thylakoid membrane. Current knowledge of the structure of PSI and PSII is based on three structures: PSI and PSII from the thermophilic cyanobacterium Thermosynechococcus elonagatus and the PSI/light harvesting complex I (PSI-LHCI) of the plant, Pisum sativum. To improve the knowledge of these important membrane protein complexes from a wider spectrum of photosynthetic organisms, photosynthetic apparatus of the thermo-acidophilic red alga, Galdieria sulphuraria and the green alga, Chlamydomonas reinhardtii were studied. Galdieria sulphuraria grows in extreme habitats such as hot sulfur springs with pH values from 0 to 4 and temperatures up to 56°C. In this study, both membrane protein complexes, PSI and PSII were isolated from this organism and characterized. Ultra-fast fluorescence spectroscopy and electron microscopy studies of PSI-LHCI supercomplexes illustrate how this organism has adapted to low light environmental conditions by tightly coupling PSI and LHC, which have not been observed in any organism so far. This result highlights the importance of structure-function relationships in different ecosystems. Galdieria sulphuraria PSII was used as a model protein to show the amenability of integral membrane proteins to top-down mass spectrometry. G.sulphuraria PSII has been characterized with unprecedented detail with identification of post translational modification of all the PSII subunits. This study is a technology advancement paving the way for the usage of top-down mass spectrometry for characterization of other large integral membrane proteins. The green alga, Chlamydomonas reinhardtii is widely used as a model for eukaryotic photosynthesis and results from this organism can be extrapolated to other eukaryotes, especially agricultural crops. Structural and functional studies on the PSI-LHCI complex of C.reinhardtii grown under high salt conditions were studied using ultra-fast fluorescence spectroscopy, circular dichroism and MALDI-TOF. Results revealed that pigment-pigment interactions in light harvesting complexes are disrupted and the acceptor side (ferredoxin docking side) is damaged under high salt conditions.
ContributorsThangaraj, Balakumar (Author) / Fromme, Petra (Thesis advisor) / Shock, Everett (Committee member) / Chen, Julian (Committee member) / Arizona State University (Publisher)
Created2010
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
Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from kerogen may have implications for research focused on the Li-isotopes of buried sediments (e.g., evaluating paleoclimate variations using marine carbonates).The objective of this work is to better understand the role of kerogen in the Li geochemical cycle. The research approach consisted of 1) developing reference materials and methodologies to measure the Li-contents and δ7Li of kerogen in-situ by Secondary Ion Mass Spectrometry, 2) surveying the Li-contents and δ7Li of kerogen bearing rocks from different depositional and diagenetic environments and 3) quantifying the Li-content and δ7Li variations in kerogen empirically in a field study and 4) experimentally through hydrous pyrolysis.
A survey of δ7Li of coals from depositional basins across the USA showed that thermally immature coals have light δ7Li values (–20 to – 10‰) compared to typical terrestrial materials (> –10‰) and the δ7Li of coal increases with burial temperature suggesting that 6Li is preferentially released from kerogen to porefluids during hydrocarbon generation. A field study was conducted on two Cretaceous coal seams in Colorado (USA) intruded by dikes (mafic and felsic) creating a temperature gradient from the intrusives into the country rock. Results showed that δ7Li values of the unmetamorphosed vitrinite macerals were up to 37‰ lighter than vitrinite macerals and coke within the contact metamorphosed coal.
To understand the significance of Li derived from kerogen during burial diagenesis, hydrous pyrolysis experiments of three coals were conducted. Results showed that Li is released from kerogen during hydrocarbon generation and could increase sedimentary porefluid Li-contents up to ~100 mg/L. The δ7Li of coals becomes heavier with increased temperature except where authigenic silicates may compete for the released Li. These results indicate that kerogen is a significant source of isotopically light Li to diagenetic fluids and is an important contributor to the global geochemical cycle.
ContributorsTeichert, Zebadiah (Author) / Williams, Lynda B. (Thesis advisor) / Bose, Maitrayee (Thesis advisor) / Hervig, Richard (Committee member) / Semken, Steven (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2022
Description
As air quality standards become more stringent to combat poor air quality, there is a greater need for more effective pollutant control measures and increased air monitoring network coverage. Polluted air, in the form of aerosols and gases, can impact respiratory and cardiovascular health, visibility, the climate, and material weathering. This work demonstrates how traditional networks can be used to study generational events, how these networks can be supplemented with low-cost sensors, and the effectiveness of several control measures. First, an existing network was used to study the effect of COVID-19 travel restrictions on air quality in Maricopa County, Arizona, which would not have been possible without the historical record that a traditional network provides. Although this study determined that decreases in CO and NO2 were not unique to the travel restrictions, it was limited to only three locations due to network sparseness. The second part of this work expanded the traditional NO2 monitoring network using low-cost sensors, that were first collocated with a reference monitor to evaluate their performance and establish a robust calibration. The sensors were then deployed to the field to varying results; their calibration was further improved by cycling the sensors between deployment and reference locations throughout the summer. This calibrated NO2 data, along with volatile organic compound data, were combined to enhance the understanding of ozone formation in Maricopa County, especially during wildfire season. In addition to being in non-attainment for ozone standards, Maricopa County fails to meet particulate matter under 10 μm (PM10) standards. A large portion of PM10 emissions is attributed to fugitive dust that is either windblown or kicked up by vehicles. The third part of this work demonstrated that Enzyme Induced Carbonate Precipitation (EICP) treatments aggregate soil particles and prevent fugitive dust emissions. The final part of the work examined tire wear PM10 emissions, as vehicles are another significant contributor to PM10. Observations showed a decrease in tire wear PM10 during winter with little change when varying the highway surface type.
ContributorsMiech, Jason Andrew (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew P (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2023
Description
The prevalence and unique properties of airborne nanoparticles have raised concerns regarding their potential adverse health effects. Despite their significance, the understanding of nanoparticle generation, transport, and exposure remains incomplete. This study first aimed to assess nanoparticle exposure in indoor workplace environments, in the semiconductor manufacturing industry. On-site observations during tool preventive maintenance revealed a significant release of particles smaller than 30 nm, which subsequent instrumental analysis confirmed as predominantly composed of transition metals. Although the measured mass concentration levels did not exceed current federal limits, it prompted concerns regarding how well filter-based air sampling methods would capture the particles for exposure assessment and how well common personal protective equipment would protect from exposure. To address these concerns, this study evaluated the capture efficiency of filters and masks. When challenged by aerosolized engineered nanomaterials, common filters used in industrial hygiene sampling exhibited capture efficiencies of over 60%. Filtering Facepiece Respirators, such as the N95 mask, exhibited a capture efficiency of over 98%. In contrast, simple surgical masks showed a capture efficiency of approximately 70%. The experiments showed that face velocity and ambient humidity influence capture performance and mostly identified the critical role of mask and particle surface charge in capturing nanoparticles. Masks with higher surface potential exhibited higher capture efficiency towards nanoparticles. Eliminating their surface charge resulted in a significantly diminished capture efficiency, up to 43%. Finally, this study characterized outdoor nanoparticle concentrations in the Phoenix metropolitan area, revealing typical concentrations on the order of 10^4 #/cm3 consistent with other urban environments. During the North American monsoon season, in dust storms, with elevated number concentrations of large particles, particularly in the size range of 1-10 μm, the number concentration of nanoparticles in the size range of 30-100 nm was substantially lower by approximately 55%. These findings provide valuable insights for future assessments of nanoparticle exposure risks and filter capture mechanisms associated with airborne nanoparticles.
ContributorsZhang, Zhaobo (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Shock, Everett (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2023
Description
Sulfur oxidation is a process that is seen a wide variety of places. One particular place is Yellowstone national park where an abundance of hot springs are present. These acidic and hot places are prime locations for sulfur oxidation to occur. At a very basic level this is thought of as Sulfur, oxygen, and water forming sulfate and hydrogen. Many other reactions occur when an organism performs these processes, and many enzymes are used for this. This paper aimed to create, balance, and analyze the reactions involved in the paper Sulfur Oxidation in the Acidophilic Autotrophic Acidithiobacillus spp. (Wang et al., 2019) Once these reactions were balanced thermodynamic properties were found to evaluate the Gibbs Free Energy of these reactions. This allowed for a unique energy-based view of how this web of reactions relate to each other.
ContributorsMolina, Johnathan (Author) / Shock, Everett (Thesis director) / Weeks, Katelyn (Committee member) / Barrett, The Honors College (Contributor) / School of Molecular Sciences (Contributor)
Created2021-12
Description
I present results of field and laboratory experiments investigating the habitability of one of Earth’s driest environments: the Atacama Desert. This Desert, along the west coast of South America spanning Perú and Chile, is one of the driest places on Earth and has been exceedingly arid for millions of years. These conditions create the perfect natural laboratory for assessing life at the extremes of habitability. All known life needs water; however, the extraordinarily dry Atacama Desert is inhabited by well-adapted microorganisms capable of colonizing this hostile environment. I show field and laboratory evidence of an environmental process, water vapor adsorption, that provides a daily, sustainable input of water into the near (3 - 5 cm) subsurface through water vapor-soil particle interactions. I estimate that this water input may rival the yearly average input of rain in these soils (~2 mm).
I also demonstrate, for the first time, that water vapor adsorption is dependent on mineral composition via a series of laboratory water vapor adsorption experiments. The results of these experiments provide evidence that mineral composition, and ultimately soil composition, measurably and significantly affect the equilibrium soil water content. This suggests that soil microbial communities may be extremely heterogeneous in distribution depending on the distribution of adsorbent minerals.
Finally, I present changes in biologically relevant gasses (i.e., H2, CH4, CO, and CO2) over long-duration incubation experiments designed to assess the potential for biological activity in soils collected from a hyperarid region in the Atacama Desert. These long-duration experiments mimicked typical water availability conditions in the Atacama Desert; in other words, the incubations were performed without condensed water addition. The results suggest a potential for methane-production in the live experiments relative to the sterile controls, and thus, for biological activity in hyperarid soils. However, due to the extremely low biomass and extremely low rates of activity in these soils, the methods employed here were unable to provide robust evidence for activity. Overall, the hyperarid regions of the Atacama Desert are an important resource for researchers by providing a window into the environmental dynamics and subsequent microbial responses near the limit of habitability.
ContributorsGlaser, Donald M (Author) / Hartnett, Hilairy E (Thesis advisor) / Anbar, Ariel (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2022