Matching Items (231)
Description
A new analytical method is proposed for measuring the deuterium to hydrogen ratio (D/H) of non-stoichiometric water in hydrous minerals via pyrolysis facilitated gas-chromatography - isotope ratio mass spectrometry (GC-IRMS). Previously published analytical methods have reported a poorly understood nonlinear dependence of D/H on sample size, for which any accurate correction is difficult. This sample size effect been variously attributed to kinetic isotope fractionation within the mass spectrometer and peripheral instruments, ion source linearity issues, and an unstable H_3^+-factor or incorrect H_3^+-factor calculations. The cause of the sample size effect is here identified by examinations of individual chromatograms as well as bulk data from chromatographic peaks. It is here determined that it is primarily an artifact of the calculations employed by the manufacturer's computer program, used to both monitor the functions of the mass spectrometer and to collect data. Ancillary causes of the sample size effect include a combination of persistent background interferences and chromatographic separation of the isotopologues of molecular hydrogen. Previously published methods are evaluated in light of these findings. A new method of H_3^+-factor and D/H calculation is proposed which makes portions of the Isodat software as well as other published calculation methods unnecessary. Using this new method, D/H is measured in non-stoichiometric water in chert from the Cretaceous Edwards Group, Texas, as well as the Precambrian Kromberg Formation, South Africa, to assess hydrological conditions as well as to estimate the maximum average surface temperature during precipitation of the chert. Data from Cretaceous chert are consistent with previously published data and interpretations, based upon conventional analyses of large samples. Data from Precambrian chert are consistent with maximum average surface temperatures approaching 65°C during the Archean, instead of the much lower temperatures derived from erroneous methods of sample preparation and analysis. D/H is likewise measured in non-stoichiometric water in silicified basalt from the Precambrian Hooggenoeg Complex, South Africa. Data are shown to be consistent with D/H of the Archean ocean similar to present day values.
ContributorsSheehan, Michael Robert (Author) / Knauth, Leroy P (Thesis advisor) / Anbar, Ariel (Committee member) / Farmer, Jack (Committee member) / Arizona State University (Publisher)
Created2011
Description
Like individual organisms, complex social groups are able to maintain predictable trajectories of growth, from initial colony foundation to mature reproductively capable units. They do so while simultaneously responding flexibly to variation in nutrient availability and intake. Leafcutter ant colonies function as tri-trophic systems, in which the ants harvest vegetation to grow a fungus that, in turn, serves as food for the colony. Fungal growth rates and colony worker production are interdependent, regulated by nutritional and behavioral feedbacks. Fungal growth and quality are directly affected by worker foraging decisions, while worker production is, in turn, dependent on the amount and condition of the fungus. In this dissertation, I first characterized the growth relationship between the workers and the fungus of the desert leafcutter ant Acromyrmex versicolor during early stages of colony development, from colony foundation by groups of queens through the beginnings of exponential growth. I found that this relationship undergoes a period of slow growth and instability when workers first emerge, and then becomes allometrically positive. I then evaluated how mass and element ratios of resources collected by the ants are translated into fungus and worker population growth, and refuse, finding that colony digestive efficiency is comparable to digestive efficiencies of other herbivorous insects and ruminants. To test how colonies behaviorally respond to perturbations of the fungus garden, I quantified activity levels and task performance of workers in colonies with either supplemented or diminished fungus gardens, and found that colonies adjusted activity and task allocation in response to the fungus garden size. Finally, to identify possible forms of nutrient limitation, I measured how colony performance was affected by changes in the relative amounts of carbohydrates, protein, and phosphorus available in the resources used to grow the fungus garden. From this experiment, I concluded that colony growth is primarily carbohydrate-limited.
ContributorsClark, Rebecca, 1981- (Author) / Fewell, Jennifer H (Thesis advisor) / Mueller, Ulrich (Committee member) / Liebig, Juergen (Committee member) / Elser, James (Committee member) / Harrison, Jon (Committee member) / Arizona State University (Publisher)
Created2011
Description
The use of synthetic cathinones or "bath salts" has risen dramatically in recent years with one of the most popular being Methylendioxypyrovalerone (MDPV). Following the temporary legislative ban on the sale and distribution of this compound , a multitude of other cathinone derivatives have been synthesized. The current study seeks to compare the abuse potential of MDPV with one of the emergent synthetic cathinones 4-methylethcathinone (4-MEC), based on their respective ability to lower current thresholds in an intracranial self-stimulation (ICSS) paradigm. Following acute administration (0.1, 0.5, 1 and 2 mg/kg i.p.) MDPV was found to significantly lower ICSS thresholds at all doses tested (F4,35=11.549, p<0.001). However, following acute administration (0.3,1,3,10,30 mg/kg i.p) 4-MEC produced no significant ICSS threshold depression (F5,135= 0.622, p = 0.684). Together these findings suggest that while MDPV may possess significant abuse potential, other synthetic cathinones such as 4-MEC may have a drastically reduced potential for abuse.
ContributorsWegner, Scott Andrew (Author) / Olive, M. Foster (Thesis director) / Presson, Clark (Committee member) / Sanabria, Federico (Committee member) / Barrett, The Honors College (Contributor) / Department of Chemistry and Biochemistry (Contributor) / Department of Psychology (Contributor)
Created2013-05
Description
Harsh environments have conditions that make collecting scientific data difficult with existing commercial-off-the-shelf technology. Micro Electro Mechanical Systems (MEMS) technology is ideally suited for harsh environment characterization and operation due to the wide range of materials available and an incredible array of different sensing techniques while providing small device size, low power consumption, and robustness. There were two main objectives of the research conducted. The first objective was to design, fabricate, and test novel sensors that measure the amount of exposure to ionizing radiation for a wide range of applications including characterization of harsh environments. Two types of MEMS ionizing radiation dosimeters were developed. The first sensor was a passive radiation-sensitive capacitor-antenna design. The antenna's emitted frequency of peak-intensity changed as exposure time to radiation increased. The second sensor was a film bulk acoustic-wave resonator, whose resonant frequency decreased with increasing ionizing radiation exposure time. The second objective was to develop MEMS sensor systems that could be deployed to gather scientific data and to use that data to address the following research question: do temperature and/or conductivity predict the appearance of photosynthetic organisms in hot springs. To this end, temperature and electrical conductivity sensor arrays were designed and fabricated based on mature MEMS technology. Electronic circuits and the software interface to the electronics were developed for field data collection. The sensor arrays utilized in the hot springs yielded results that support the hypothesis that temperature plays a key role in determining where the photosynthetic organisms occur. Additionally, a cold-film fluidic flow sensor was developed, which is suitable for near-boiling temperature measurement. Future research should focus on (1) developing a MEMS pH sensor array with integrated temperature, conductivity, and flow sensors to provide multi-dimensional data for scientific study and (2) finding solutions to biofouling and self-calibration, which affects sensor performance over long-term deployment.
ContributorsOiler, Jonathon (Author) / Yu, Hongyu (Thesis advisor) / Anbar, Ariel (Committee member) / Hartnett, Hilairy (Committee member) / Scannapieco, Evan (Committee member) / Timmes, Francis (Committee member) / Arizona State University (Publisher)
Created2013
Description
The presence of a number of extinct radionuclides in the early Solar System (SS) is known from geochemical and isotopic studies of meteorites and their components. The half-lives of these isotopes are short relative to the age of the SS, such that they have now decayed to undetectable levels. They can be inferred to exist in the early SS from the presence of their daughter nuclides in meteoritic materials that formed while they were still extant. The extinct radionuclides are particularly useful as fine-scale chronometers for events in the early SS. They can also be used to help constrain the astrophysical setting of the formation of the SS because their short half-lives and unique formation environments yield information about the sources and timing of delivery of material to the protoplanetary disk. Some extinct radionuclides are considered evidence that the Sun interacted with a massive star (supernova) early in its history. The abundance of 60Fe in the early SS is particularly useful for constraining the astrophysical environment of the Sun's formation because, if present in sufficient abundance, its only likely source is injection from a nearby supernova. The initial SS abundance of 60Fe is poorly constrained at the present time, with estimates varying by 1-2 orders of magnitude. I have determined the 60Fe-60Ni isotope systematics of ancient, well-preserved meteorites using high-precision mass spectrometry to better constrain the initial SS abundance of 60Fe. I find identical estimates of the initial 60Fe abundance from both differentiated basaltic meteorites and from components of primitive chondrites formed in the Solar nebula, which suggest a lower 60Fe abundance than other recent estimates. With recent improved meteorite collection efforts there are more rare ungrouped meteorites being found that hold interesting clues to the origin and evolution of early SS objects. I use the 26Al-26Mg extinct radionuclide chronometer to constrain the ages of several recently recovered meteorites that sample previously unknown asteroid lithologies, including the only know felsic meteorite from an asteroid and two other ungrouped basaltic achondrites. These results help broaden our understanding of the timescales involved in igneous differentiation processes in the early SS.
ContributorsSpivak-Birndorf, Lev (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Timmes, Francis (Committee member) / Williams, Lynda (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2012
Description
The only elements that were made in significant quantity during the Big Bang were hydrogen and helium, and to a lesser extent lithium. Depending on the initial mass of a star, it may eject some or all of the unique, newly formed elements into the interstellar medium. The enriched gas later collapses into new stars, which are able to form heavier elements due to the presence of the new elements. When we observe the abundances in a stellar regions, we are able to glean the astrophysical phenomena that occurred prior to its formation. I compile spectroscopic abundance data from 49 literature sources for 46 elements across 2836 stars in the solar neighborhood, within 150 pc of the Sun, to produce the Hypatia Catalog. I analyze the variability of the spread in abundance measurements reported for the same star by different surveys, the corresponding stellar atmosphere parameters adopted by various abundance determination methods, and the effect of normalizing all abundances to the same solar scale. The resulting abundance ratios [X/Fe] as a function of [Fe/H] are consistent with stellar nucleosynthetic processes and known Galactic thin-disk trends. I analyze the element abundances for 204 known exoplanet host-stars. In general, I find that exoplanet host-stars are not enriched more than the surrounding population of stars, with the exception of iron. I examine the stellar abundances with respect to both stellar and planetary physical properties, such as orbital period, eccentricity, planetary mass, stellar mass, and stellar color. My data confirms that exoplanet hosts are enriched in [Fe/H] but not in the refractory elements, per the self-enrichment theory for stellar composition. Lastly, I apply the Hypatia Catalog to the Catalog of Potentially Habitable Stellar Systems in order to investigate the abundances in the 1224 overlapping stars. By looking at stars similar to the Sun with respect to six bio-essential elements, I created maps that have located two ``habitability windows'' on the sky: (20.6hr, -4.8deg) and (22.6hr, -48.5deg). These windows may be of use in future targeted or beamed searches.
ContributorsHinkel, Natalie R (Author) / Timmes, Frank X (Thesis advisor) / Anbar, Ariel (Committee member) / Patience, Jennifer (Committee member) / Shumway, John (Committee member) / Young, Patrick (Committee member) / Arizona State University (Publisher)
Created2012
Description
Land management practices such as domestic animal grazing can alter plant communities via changes in soil structure and chemistry, species composition, and plant nutrient content. These changes can affect the abundance and quality of plants consumed by insect herbivores with consequent changes in population dynamics. These population changes can translate to massive crop damage and pest control costs. My dissertation focused on Oedaleus asiaticus, a dominant Asian locust, and had three main objectives. First, I identified morphological, physiological, and behavioral characteristics of the migratory ("brown") and non-migratory ("green") phenotypes. I found that brown morphs had longer wings, larger thoraxes and higher metabolic rates compared to green morphs, suggesting that developmental plasticity allows greater migratory capacity in the brown morph of this locust. Second, I tested the hypothesis of a causal link between livestock overgrazing and an increase in migratory swarms of O. asiaticus. Current paradigms generally assume that increased plant nitrogen (N) should enhance herbivore performance by relieving protein-limitation, increasing herbivorous insect populations. I showed, in contrast to this scenario, that host plant N-enrichment and high protein artificial diets decreased the size and viability of O. asiaticus. Plant N content was lowest and locust abundance highest in heavily livestock-grazed fields where soils were N-depleted, likely due to enhanced erosion and leaching. These results suggest that heavy livestock grazing promotes outbreaks of this locust by reducing plant protein content. Third, I tested for the influence of dietary imbalance, in conjunction with high population density, on migratory plasticity. While high population density has clearly been shown to induce the migratory morph in several locusts, the effect of diet has been unclear. I found that locusts reared at high population density and fed unfertilized plants (i.e. high quality plants for O. asiaticus) had the greatest migratory capacity, and maintained a high percent of brown locusts. These results did not support the hypothesis that poor-quality resources increased expression of migratory phenotypes. This highlights a need to develop new theoretical frameworks for predicting how environmental factors will regulate migratory plasticity in locusts and perhaps other insects.
ContributorsCease, Arianne (Author) / Harrison, Jon (Thesis advisor) / Elser, James (Thesis advisor) / DeNardo, Dale (Committee member) / Quinlan, Michael (Committee member) / Sabo, John (Committee member) / Arizona State University (Publisher)
Created2012
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
Many studies over the past two decades examined the link between climate patterns and discharge, but few have attempted to study the effects of the El Niño Southern Oscillation (ENSO) on localized and watershed specific processes such as nutrient loading in the Southwestern United States. The Multivariate ENSO Index (MEI) is used to describe the state of the ENSO, with positive (negative) values referring to an El Niño condition (La Niña condition). This study examined the connection between the MEI and precipitation, discharge, and total nitrogen (TN) and total phosphorus (TP) concentrations in the Upper Salt River Watershed in Arizona. Unrestricted regression models (UMs) and restricted regression models (RMs) were used to investigate the relationship between the discharges in Tonto Creek and the Salt River as functions of the magnitude of the MEI, precipitation, and season (winter/summer). The results suggest that in addition to precipitation, the MEI/season relationship is an important factor for predicting discharge. Additionally, high discharge events were associated with high magnitude ENSO events, both El Niño and La Niña. An UM including discharge and season, and a RM (restricting the seasonal factor to zero), were applied to TN and TP concentrations in the Salt River. Discharge and seasonality were significant factors describing the variability in TN in the Salt River while discharge alone was the significant factor describing TP. TN and TP in Roosevelt Lake were evaluated as functions of both discharge and MEI. Some significant correlations were found but internal nutrient cycling as well as seasonal stratification of the water column of the lake likely masks the true relationships. Based on these results, the MEI is a useful predictor of discharge, as well as nutrient loading in the Salt River Watershed through the Salt River and Tonto Creek. A predictive model investigating the effect of ENSO on nutrient loading through discharge can illustrate the effects of large scale climate patterns on smaller systems.
ContributorsSversvold, Darren (Author) / Neuer, Susanne (Thesis advisor) / Elser, James (Committee member) / Fenichel, Eli (Committee member) / Arizona State University (Publisher)
Created2012
Description
Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding of the diagenetic processes that may affect molybdenum and uranium isotopes entering the rock record. Using samples from the Black Sea water column, the first water column profile of 238U/235U variations from a modern euxinic basin has been measured. This profile allows the direct determination of the 238U/235U fractionation factor in a euxinic marine setting. More importantly however, these data demonstrate the extent of Rayleigh fractionation of U isotopes that can occur in euxinic restricted basins. Because of this effect, the offset of 238U/235U between global average seawater and coeval black shales deposited in restricted basins is expected to depend on the degree of local uranium drawdown from the water column, potentially complicating the interpretation 238U/235U paleorecords. As an alternative to the black shales typically used for paleoredox reconstructions, molybdenum and uranium isotope variations in bulk carbonate sediments from the Bahamas are examined. The focus of this work was to determine what processes, if any, fractionate molybdenum and uranium isotopes during incorporation into bulk carbonate sediments and their subsequent diagenesis. The results demonstrate that authigenic accumulation of molybdenum and uranium from anoxic and sulfidic pore waters is a dominant process controlling the concentration and isotopic composition of these sediments during early diagenesis. Examination of ODP drill core samples from the Bahamas reveals similar behavior for sediments during the first ~780ka of burial, but provides important examples where isolated cores and samples occasionally demonstrate additional fractionation, the cause of which remains poorly understood.
ContributorsRomaniello, Stephen J. (Author) / Anbar, Ariel (Thesis advisor) / Hartnett, Hilairy (Committee member) / Herrmann, Achim (Committee member) / Shock, Everett (Committee member) / Wadhwa, Meenakshi (Committee member) / Arizona State University (Publisher)
Created2012