Matching Items (239)
Description
Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are essential for interpreting Martian mineralogy and geologic history. However, previous studies have shown that chemical weathering and the precipitation of fine-grained secondary silicates can adversely affect the accuracy of TIR spectral models. Furthermore, spectral libraries used to identify minerals on the Martian surface lack some important weathering products, including poorly-crystalline aluminosilicates like allophane, thus eliminating their identification in TIR spectral models. It is essential to accurately interpret TIR spectral data from chemically weathered surfaces to understand the evolution of aqueous processes on Mars. Laboratory experiments were performed to improve interpretations of TIR data from weathered surfaces. To test the accuracy of deriving chemistry of weathered rocks from TIR spectroscopy, chemistry was derived from TIR models of weathered basalts from Baynton, Australia and compared to actual weathering rind chemistry. To determine how specific secondary silicates affect the TIR spectroscopy of weathered basalts, mixtures of basaltic minerals and small amounts of secondary silicates were modeled. Poorly-crystalline aluminosilicates were synthesized and their TIR spectra were added to spectral libraries. Regional Thermal Emission Spectrometer (TES) data were modeled using libraries containing these poorly-crystalline aluminosilicates to test for their presence on the Mars. Chemistry derived from models of weathered Baynton basalts is not accurate, but broad chemical weathering trends can be interpreted from the data. TIR models of mineral mixtures show that small amounts of crystalline and amorphous silicate weathering products (2.5-5 wt.%) can be detected in TIR models and can adversely affect modeled plagioclase abundances. Poorly-crystalline aluminosilicates are identified in Northern Acidalia, Solis Planum, and Meridiani. Previous studies have suggested that acid sulfate weathering was the dominant surface alteration process for the past 3.5 billion years; however, the identification of allophane indicates that alteration at near-neutral pH occurred on regional scales and that acid sulfate weathering is not the only weathering process on Mars.
ContributorsRampe, Elizabeth Barger (Author) / Sharp, Thomas G (Thesis advisor) / Christensen, Phillip (Committee member) / Hervig, Richard (Committee member) / Shock, Everett (Committee member) / Williams, Lynda (Committee member) / Arizona State University (Publisher)
Created2011
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
Infections caused by the Hepatitis C Virus (HCV) are very common worldwide, affecting up to 3% of the population. Chronic infection of HCV may develop into liver cirrhosis and liver cancer which is among the top five of the most common cancers. Therefore, vaccines against HCV are under intense study in order to prevent HCV from harming people's health. The envelope protein 2 (E2) of HCV is thought to be a promising vaccine candidate because it can directly bind to a human cell receptor and plays a role in viral entry. However, the E2 protein production in cells is inefficient due to its complicated matured structure. Folding of E2 in the endoplasmic reticulum (ER) is often error-prone, resulting in production of aggregates and misfolded proteins. These incorrect forms of E2 are not functional because they are not able to bind to human cells and stimulate antibody response to inhibit this binding. This study is aimed to overcome the difficulties of HCV E2 production in plant system. Protein folding in the ER requires great assistance from molecular chaperones. Thus, in this study, two molecular chaperones in the ER, calreticulin and calnexin, were transiently overexpressed in plant leaves in order to facilitate E2 folding and production. Both of them showed benefits in increasing the yield of E2 and improving the quality of E2. In addition, poorly folded E2 accumulated in the ER may cause stress in the ER and trigger transcriptional activation of ER molecular chaperones. Therefore, a transcription factor involved in this pathway, named bZIP60, was also overexpressed in plant leaves, aiming at up-regulating a major family of molecular chaperones called BiP to assist protein folding. However, our results showed that BiP mRNA levels were not up-regulated by bZIP60, but they increased in response to E2 expression. The Western blot analysis also showed that overexpression of bZIP60 had a small effect on promoting E2 folding. Overall, this study suggested that increasing the level of specific ER molecular chaperones was an effective way to promote HCV E2 protein production and maturation.
ContributorsHong, Fan (Author) / Mason, Hugh (Thesis advisor) / Gaxiola, Roberto (Committee member) / Chang, Yung (Committee member) / Chen, Qiang (Committee member) / Arizona State University (Publisher)
Created2011
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
A new challenge on the horizon is to utilize the large amounts of protein found in the atmosphere to identify different organisms from which the protein originated. Included here is work investigating the presence of identifiable patterns of different proteins collected from the air and biological samples for the purposes of remote identification. Protein patterns were generated using high performance liquid chromatography (HPLC). Patterns created could identify high-traffic and low-traffic indoor spaces. Samples were collected from the air using air pumps to draw air through a filter paper trapping particulates, including large amounts of shed protein matter. In complimentary research aerosolized biological samples were collected from various ecosystems throughout Ecuador to explore the relationship between environmental setting and aerosolized protein concentrations. In order to further enhance protein separation and produce more detailed patterns for the identification of individual organisms of interest; a novel separation device was constructed and characterized. The separation device incorporates a longitudinal gradient as well as insulating dielectrophoretic features within a single channel. This design allows for the production of stronger local field gradients along a global gradient allowing particles to enter, initially transported through the channel by electrophoresis and electroosmosis, and to be isolated according to their characteristic physical properties, including charge, polarizability, deformability, surface charge mobility, dielectric features, and local capacitance. Thus, different types of particles are simultaneously separated at different points along the channel distance given small variations of properties. The device has shown the ability to separate analytes over a large dynamic range of size, from 20 nm to 1 μm, roughly the size of proteins to the size of cells. In the study of different sized sulfate capped polystyrene particles were shown to be selectively captured as well as concentrating particles from 103 to 106 times. Qualitative capture and manipulation of β-amyloid fibrils were also shown. The results demonstrate the selective focusing ability of the technique; and it may form the foundation for a versatile tool for separating complex mixtures. Combined this work shows promise for future identification of individual organisms from aerosolized protein as well as for applications in biomedical research.
ContributorsStaton, Sarah J. R (Author) / Hayes, Mark A. (Committee member) / Anbar, Ariel D (Committee member) / Shock, Everett (Committee member) / Williams, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the relative abundance of constituents, favorable photovoltaic properties, and good lattice matching with ZnSnP2, the other component in this tandem device. This work is divided into two main chapters, which will cover: calculations and method to determine the formation energy and abundance of native point defects, and a model to calculate the vapor pressure over a ternary material from first-principles. The purpose of this work is to guide experimental work being done in tandem to synthesize ZnGeAs2 in thin-film form with high enough quality such that it can be used as a photovoltaic. Since properties of photovoltaic depend greatly on defect concentrations and film quality, a theoretical understanding of how laboratory conditions affect these properties is very valuable. The work done here is from first-principles and utilizes density functional theory using the local density approximation. Results from the native point defect study show that the zinc vacancy (VZn) and the germanium antisite (GeZn) are the more prominent defects; which most likely produce non-stoichiometric films. The vapor pressure model for a ternary system is validated using known vapor pressure for monatomic and binary test systems. With a valid ternary system vapor pressure model, results show there is a kinetic barrier to decomposition for ZnGeAs2.
ContributorsTucker, Jon R (Author) / Van Schilfgaarde, Mark (Thesis advisor) / Newman, Nathan (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2011
Description
Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.
ContributorsKilgore, Stephen (Author) / Adams, James (Thesis advisor) / Schroder, Dieter (Thesis advisor) / Krause, Stephen (Committee member) / Gaw, Craig (Committee member) / Arizona State University (Publisher)
Created2013
Description
Surface plasmon resonance (SPR) has emerged as a popular technique for elucidating subtle signals from biological events in a label-free, high throughput environment. The efficacy of conventional SPR sensors, whose signals are mass-sensitive, diminishes rapidly with the size of the observed target molecules. The following work advances the current SPR sensor paradigm for the purpose of small molecule detection. The detection limits of two orthogonal components of SPR measurement are targeted: speed and sensitivity. In the context of this report, speed refers to the dynamic range of measured kinetic rate constants, while sensitivity refers to the target molecule mass limitation of conventional SPR measurement. A simple device for high-speed microfluidic delivery of liquid samples to a sensor surface is presented to address the temporal limitations of conventional SPR measurement. The time scale of buffer/sample switching is on the order of milliseconds, thereby minimizing the opportunity for sample plug dispersion. The high rates of mass transport to and from the central microfluidic sensing region allow for SPR-based kinetic analysis of binding events with dissociation rate constants (kd) up to 130 s-1. The required sample volume is only 1 μL, allowing for minimal sample consumption during high-speed kinetic binding measurement. Charge-based detection of small molecules is demonstrated by plasmonic-based electrochemical impedance microscopy (P-EIM). The dependence of surface plasmon resonance (SPR) on surface charge density is used to detect small molecules (60-120 Da) printed on a dextran-modified sensor surface. The SPR response to an applied ac potential is a function of the surface charge density. This optical signal is comprised of a dc and an ac component, and is measured with high spatial resolution. The amplitude and phase of local surface impedance is provided by the ac component. The phase signal of the small molecules is a function of their charge status, which is manipulated by the pH of a solution. This technique is used to detect and distinguish small molecules based on their charge status, thereby circumventing the mass limitation (~100 Da) of conventional SPR measurement.
ContributorsMacGriff, Christopher Assiff (Author) / Tao, Nongjian (Thesis advisor) / Wang, Shaopeng (Committee member) / LaBaer, Joshua (Committee member) / Chae, Junseok (Committee member) / Arizona State University (Publisher)
Created2013
Description
Stable isotopes were measured in the groundwaters of the Salt River Valley basin in central Arizona to explore the utility of stable isotopes for sourcing recharge waters and engineering better well designs. Delta values for the sampled groundwaters range from -7.6‰ to -10‰ in 18O and -60‰ to -91‰ in D and display displacements off the global meteoric water line indicative of surficial evaporation during river transport into the area. Groundwater in the basin is all derived from top-down river recharge; there is no evidence of ancient playa waters even in the playa deposits. The Salt and Verde Rivers are the dominant source of groundwater for the East Salt River valley- the Agua Fria River also contributes significantly to the West Salt River Valley. Groundwater isotopic compositions are generally more depleted in 18O and D with depth, indicating past recharge in cooler climates, and vary within subsurface aquifer layers as sampled during well drilling. When isotopic data were evaluated together with geologic and chemical analyses and compared with data from the final well production water it was often possible to identify: 1) which horizons are the primary producers of groundwater flow and how that might change with time, 2) the chemical exchange of cations and anions via water-rock interaction during top-down mixing of recharge water with older waters, 3) how much well production might be lost if arsenic-contributing horizons were sealed off, and 4) the extent to which replacement wells tap different subsurface water sources. In addition to identifying sources of recharge, stable isotopes offer a new and powerful approach for engineering better and more productive water wells.
ContributorsBond, Angela Nicole (Author) / Knauth, Paul (Thesis advisor) / Hartnett, Hilairy (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2010
Description
Microbially induced calcium carbonate precipitation (MICP) is attracting increasing attention as a sustainable means of soil improvement. While there are several possible MICP mechanisms, microbial denitrification has the potential to become one of the preferred methods for MICP because complete denitrification does not produce toxic byproducts, readily occurs under anoxic conditions, and potentially has a greater carbonate yield per mole of organic electron donor than other MICP processes. Denitrification may be preferable to ureolytic hydrolysis, the MICP process explored most extensively to date, as the byproduct of denitrification is benign nitrogen gas, while the chemical pathways involved in hydrolytic ureolysis processes produce undesirable and potentially toxic byproducts such as ammonium (NH4+). This thesis focuses on bacterial denitrification and presents preliminary results of bench-scale laboratory experiments on denitrification as a candidate calcium carbonate precipitation mechanism. The bench-scale bioreactor and column tests, conducted using the facultative anaerobic bacterium Pseudomonas denitrificans, show that calcite can be precipitated from calcium-rich pore water using denitrification. Experiments also explore the potential for reducing environmental impacts and lowering costs associated with denitrification by reducing the total dissolved solids in the reactors and columns, optimizing the chemical matrix, and addressing the loss of free calcium in the form of calcium phosphate precipitate from the pore fluid. The potential for using MICP to sequester radionuclides and metal contaminants that are migrating in groundwater is also investigated. In the sequestration process, divalent cations and radionuclides are incorporated into the calcite structure via substitution, forming low-strontium calcium carbonate minerals that resist dissolution at a level similar to that of calcite. Work by others using the bacterium Sporosarcina pasteurii has suggested that in-situ sequestration of radionuclides and metal contaminants can be achieved through MICP via hydrolytic ureolysis. MICP through bacterial denitrification seems particularly promising as a means for sequestering radionuclides and metal contaminants in anoxic environments due to the anaerobic nature of the process and the ubiquity of denitrifying bacteria in the subsurface.
ContributorsHamdan, Nasser (Author) / Kavazanjian, Edward (Thesis advisor) / Rittmann, Bruce E. (Thesis advisor) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2013