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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
Diseases have been part of human life for generations and evolve within the population, sometimes dying out while other times becoming endemic or the cause of recurrent outbreaks. The long term influence of a disease stems from different dynamics within or between pathogen-host, that have been analyzed and studied by many researchers using mathematical models. Co-infection with different pathogens is common, yet little is known about how infection with one pathogen affects the host's immunological response to another. Moreover, no work has been found in the literature that considers the variability of the host immune health or that examines a disease at the population level and its corresponding interconnectedness with the host immune system. Knowing that the spread of the disease in the population starts at the individual level, this thesis explores how variability in immune system response within an endemic environment affects an individual's vulnerability, and how prone it is to co-infections. Immunology-based models of Malaria and Tuberculosis (TB) are constructed by extending and modifying existing mathematical models in the literature. The two are then combined to give a single nine-variable model of co-infection with Malaria and TB. Because these models are difficult to gain any insight analytically due to the large number of parameters, a phenomenological model of co-infection is proposed with subsystems corresponding to the individual immunology-based model of a single infection. Within this phenomenological model, the variability of the host immune health is also incorporated through three different pathogen response curves using nonlinear bounded Michaelis-Menten functions that describe the level or state of immune system (healthy, moderate and severely compromised). The immunology-based models of Malaria and TB give numerical results that agree with the biological observations. The Malaria--TB co-infection model gives reasonable results and these suggest that the order in which the two diseases are introduced have an impact on the behavior of both. The subsystems of the phenomenological models that correspond to a single infection (either of Malaria or TB) mimic much of the observed behavior of the immunology-based counterpart and can demonstrate different behavior depending on the chosen pathogen response curve. In addition, varying some of the parameters and initial conditions in the phenomenological model yields a range of topologically different mathematical behaviors, which suggests that this behavior may be able to be observed in the immunology-based models as well. The phenomenological models clearly replicate the qualitative behavior of primary and secondary infection as well as co-infection. The mathematical solutions of the models correspond to the fundamental states described by immunologists: virgin state, immune state and tolerance state. The phenomenological model of co-infection also demonstrates a range of parameter values and initial conditions in which the introduction of a second disease causes both diseases to grow without bound even though those same parameters and initial conditions did not yield unbounded growth in the corresponding subsystems. This results applies to all three states of the host immune system. In terms of the immunology-based system, this would suggest the following: there may be parameter values and initial conditions in which a person can clear Malaria or TB (separately) from their system but in which the presence of both can result in the person dying of one of the diseases. Finally, this thesis studies links between epidemiology (population level) and immunology in an effort to assess the impact of pathogen's spread within the population on the immune response of individuals. Models of Malaria and TB are proposed that incorporate the immune system of the host into a mathematical model of an epidemic at the population level.
ContributorsSoho, Edmé L (Author) / Wirkus, Stephen (Thesis advisor) / Castillo-Chavez, Carlos (Thesis advisor) / Chowell-Puente, Gerardo (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
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
Description
Solution methods for certain linear and nonlinear evolution equations are presented in this dissertation. Emphasis is placed mainly on the analytical treatment of nonautonomous differential equations, which are challenging to solve despite the existent numerical and symbolic computational software programs available. Ideas from the transformation theory are adopted allowing one to solve the problems under consideration from a non-traditional perspective. First, the Cauchy initial value problem is considered for a class of nonautonomous and inhomogeneous linear diffusion-type equation on the entire real line. Explicit transformations are used to reduce the equations under study to their corresponding standard forms emphasizing on natural relations with certain Riccati(and/or Ermakov)-type systems. These relations give solvability results for the Cauchy problem of the parabolic equation considered. The superposition principle allows to solve formally this problem from an unconventional point of view. An eigenfunction expansion approach is also considered for this general evolution equation. Examples considered to corroborate the efficacy of the proposed solution methods include the Fokker-Planck equation, the Black-Scholes model and the one-factor Gaussian Hull-White model. The results obtained in the first part are used to solve the Cauchy initial value problem for certain inhomogeneous Burgers-type equation. The connection between linear (the Diffusion-type) and nonlinear (Burgers-type) parabolic equations is stress in order to establish a strong commutative relation. Traveling wave solutions of a nonautonomous Burgers equation are also investigated. Finally, it is constructed explicitly the minimum-uncertainty squeezed states for quantum harmonic oscillators. They are derived by the action of corresponding maximal kinematical invariance group on the standard ground state solution. It is shown that the product of the variances attains the required minimum value only at the instances that one variance is a minimum and the other is a maximum, when the squeezing of one of the variances occurs. Such explicit construction is possible due to the relation between the diffusion-type equation studied in the first part and the time-dependent Schrodinger equation. A modication of the radiation field operators for squeezed photons in a perfect cavity is also suggested with the help of a nonstandard solution of Heisenberg's equation of motion.
ContributorsVega-Guzmán, José Manuel, 1982- (Author) / Sulov, Sergei K (Thesis advisor) / Castillo-Chavez, Carlos (Thesis advisor) / Platte, Rodrigo (Committee member) / Chowell-Puente, Gerardo (Committee member) / Arizona State University (Publisher)
Created2013
Description
Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients, such as iron, copper, and molybdenum. This work investigated the effects of BSC activity on soil solution concentrations of bioessential elements and examined the microbial production of organic chelators, called siderophores. I found that aluminum, vanadium, copper, zinc, and molybdenum were solubilized in the action of crusts, while nickel, zinc, arsenic, and zirconium were immobilized by crust activity. Potassium and manganese displayed behavior consistent with biological removal and mobilization, whereas phosphorus and iron solubility were dominated by abiotic processes. The addition of bioavailable nitrogen altered the effects of BSCs on soil element mobilization. In addition, I found that the biogeochemical activites of BSCs were limited by molybdenum, a fact that likely contributes to co-limitation by nitrogen. I confirmed the presence of siderophore producing microbes in BSCs. Siderophores are low-molecular weight organic compounds that are released by bacteria to increase element solubility and facilitate element uptake; siderophore production is likely the mechanism by which BSCs affect the patterns I observed in soil solution element concentrations. Siderophore producers were distributed across a range of bacterial groups and ecological niches within crusts, suggesting that siderophore production influences the availability of a variety of elements for use in many physiological processes. Four putative siderophore compounds were identified using electrospray ionization mass spectrometry; further attempts to characterize the compounds confirmed two true siderophores. Taken together, the results of my work provide information about micronutrient cycling within crusts that can be applied to BSC conservation and management. Fertilization with certain elements, particularly molybdenum, may prove to be a useful technique to promote BSC growth and development which would help prevent arid land degradation. Furthermore, understanding the effects of BSCs on soil element mobility could be used to develop useful biomarkers for the study of the existence and distribution of crust-like communities on ancient Earth, and perhaps other places, like Mars.
ContributorsNoonan, Kathryn Alexander (Author) / Hartnett, Hilairy (Thesis advisor) / Anbar, Ariel (Committee member) / Garcia-Pichel, Ferran (Committee member) / Shock, Everett (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2012
Description
Ponderosa pine forests are a dominant land cover type in semiarid montane areas. Water supplies in major rivers of the southwestern United States depend on ponderosa pine forests since these ecosystems: (1) receive a significant amount of rainfall and snowfall, (2) intercept precipitation and transpire water, and (3) indirectly influence runoff by impacting the infiltration rate. However, the hydrologic patterns in these ecosystems with strong seasonality are poorly understood. In this study, we used a distributed hydrologic model evaluated against field observations to improve our understandings on spatial controls of hydrologic patterns, appropriate model resolution to simulate ponderosa pine ecosystems and hydrologic responses in the context of contrasting winter to summer transitions. Our modeling effort is focused on the hydrologic responses during the North American Monsoon (NAM), winter and spring periods. In Chapter 2, we utilized a distributed model explore the spatial controls on simulated soil moisture and temporal evolution of these spatial controls as a function of seasonal wetness. Our findings indicate that vegetation and topographic curvature are spatial controls. Vegetation controlled patterns during dry summer period switch to fine-scale terrain curvature controlled patterns during persistently wet NAM period. Thus, a climatic threshold involving rainfall and weather conditions during the NAM is identified when high rainfall amount (such as 146 mm rain in August, 1997) activates lateral flux of soil moisture and frequent cloudy cover (such as 42% cloud cover during daytime of August, 1997) lowers evapotranspiration. In Chapter 3, we investigate the impacts of model coarsening on simulated soil moisture patterns during the NAM. Results indicate that model aggregation quickly eradicates curvature features and its spatial control on hydrologic patterns. A threshold resolution of ~10% of the original terrain is identified through analyses of homogeneity indices, correlation coefficients and spatial errors beyond which the fidelity of simulated soil moisture is no longer reliable. Based on spatial error analyses, we detected that the concave areas (~28% of hillslope) are very sensitive to model coarsening and root mean square error (RMSE) is higher than residual soil moisture content (~0.07 m3/m3 soil moisture) for concave areas. Thus, concave areas need to be sampled for capturing appropriate hillslope response for this hillslope. In Chapter 4, we investigate the impacts of contrasting winter to summer transitions on hillslope hydrologic responses. We use a distributed hydrologic model to generate a consistent set of high-resolution hydrologic estimates. Our model is evaluated against the snow depth, soil moisture and runoff observations over two water years yielding reliable spatial distributions during the winter to summer transitions. We find that a wet winter followed by a dry summer promotes evapotranspiration losses (spatial averaged ~193 mm spring ET and ~ 600 mm summer ET) that dry the soil and disconnect lateral fluxes in the forested hillslope, leading to soil moisture patterns resembling vegetation patches. Conversely, a dry winter prior to a wet summer results in soil moisture increases due to high rainfall and low ET during the spring (spatially averaged 78 mm ET and 232 mm rainfall) and summer period (spatially averaged 147 mm ET and 247 mm rainfall) which promote lateral connectivity and soil moisture patterns with the signature of terrain curvature. An opposing temporal switch between infiltration and saturation excess runoff is also identified. These contrasting responses indicate that the inverse relation has significant consequences on hillslope water availability and its spatial distribution with implications on other ecohydrological processes including vegetation phenology, groundwater recharge and geomorphic development. Results from this work have implications on the design of hillslope experiments, the resolution of hillslope scale models, and the prediction of hydrologic conditions in ponderosa pine ecosystems. In addition, our findings can be used to select future hillslope sites for detailed ecohydrological investigations. Further, the proposed methodology can be useful for predicting responses to climate and land cover changes that are anticipated for the southwestern United States.
ContributorsMahmood, Taufique Hasan (Author) / Vivoni, Enrique R. (Thesis advisor) / Whipple, Kelin X. (Committee member) / Shock, Everett (Committee member) / Heimsath, Arjun M. (Committee member) / Ruddell, Benjamin (Committee member) / Arizona State University (Publisher)
Created2012