Global pressures, specific responses: effects of nutrient enrichment in streams from different biomes

13 p. + 2 p. (Erratum)

Quality changes in canned tilapia stored at ambient and accelerated temperatures

Changes in the quality of canned tilapia packed in oil and tomato sauce at ambient and accelerated temperatures were examined by microbiological and sensory evaluation. Canned tilapia were found to be microbiologically stable and organoleptically acceptable after six months storage period. Total viable count (TVC) were generally low (2.5 x 10 super(2)). Thermophilic organisms (Clostridium) were absent in all samples. The yield of edible part of tilapia was 72% after dressing. Pre-cooking of tilapia resulted in a loss of 21.5% of its dressed weight. Comparison of canned tilapia with available canned fishes (geisha and bonga) showed similar trends in the taste, proximate composition, microbiological stability and sensory scores.The possibility for investment in tilapia cannary was also investigated. It was found that production of canned tilapia will be economically viable if a ten hectare tilapia farm is used as a source of raw materials.

Pressures on the biota in the aquatic ecosystem of (Chi) Cross River National Park, Okwango Division

A preliminary survey of Cross River National Park (Nigeria), Okwangwo Division was carried out. The combined natural and human pressures being exerted on the aquatic resources were also investigated. Information on the existing fishing communities in and around the park area are given. The fishermen, their fishing methods and fishing grounds were identified. Limiting factors (natural and human) to the fisheries production, are analysed. Positive measures for conservation, protection and management of healthy and natural aquatic environment are suggested

Studies of ambient and chamber aerosol composition using the aerosol mass spectrometer

This thesis presents composition measurements for atmospherically relevant inorganic and organic aerosol from laboratory and ambient measurements using the Aerodyne aerosol mass spectrometer. Studies include the oxidation of dodecane in the Caltech environmental chambers, and several aircraft- and ground-based field studies, which include the quantification of wildfire emissions off the coast of California, and Los Angeles urban emissions.

The oxidation of dodecane by OH under low NO conditions and the formation of secondary organic aerosol (SOA) was explored using a gas-phase chemical model, gas-phase CIMS measurements, and high molecular weight ion traces from particle- phase HR-TOF-AMS mass spectra. The combination of these measurements support the hypothesis that particle-phase chemistry leading to peroxyhemiacetal formation is important. Positive matrix factorization (PMF) was applied to the AMS mass spectra which revealed three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition.

Airborne measurements of biomass burning emissions from a chaparral fire on the central Californian coast were carried out in November 2009. Physical and chemical changes were reported for smoke ages 0 – 4 h old. CO₂ normalized ammonium, nitrate, and sulfate increased, whereas the normalized OA decreased sharply in the first 1.5 - 2 h, and then slowly increased for the remaining 2 h (net decrease in normalized OA). Comparison to wildfire samples from the Yucatan revealed that factors such as relative humidity, incident UV radiation, age of smoke, and concentration of emissions are important for wildfire evolution.

Ground-based aerosol composition is reported for Pasadena, CA during the summer of 2009. The OA component, which dominated the submicron aerosol mass, was deconvolved into hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low-volatility oxidized organic aerosol (LVOOA). The HOA/OA was only 0.08–0.23, indicating that most of Pasadena OA in the summer months is dominated by oxidized OA resulting from transported emissions that have undergone photochemistry and/or moisture-influenced processing, as apposed to only primary organic aerosol emissions. Airborne measurements and model predictions of aerosol composition are reported for the 2010 CalNex field campaign.

Liquid silicate equation of state : using shock waves to understand the properties of the deep Earth

The equations of state (EOS) of several geologically important silicate liquids have been constrained via preheated shock wave techniques. Results on molten Fe₂SiO₄ (fayalite), Mg₂SiO₄ (forsterite), CaFeSi₂O₆ (hedenbergite), an equimolar mixture of CaAl₂Si₂O₈-CaFeSi₂O₆ (anorthite-hedenbergite), and an equimolar mixture of CaAl₂Si₂O₈-CaFeSi₂O₆-CaMgSi₂O₆(anorthite-hedenbergite-diopside) are presented. This work represents the first ever direct EOS measurements of an iron-bearing liquid or of a forsterite liquid at pressures relevant to the deep Earth (> 135 GPa). Additionally, revised EOS for molten CaMgSi₂O₆ (diopside), CaAl₂Si₂O₈ (anorthite), and MgSiO₃ (enstatite), which were previously determined by shock wave methods, are also presented.

The liquid EOS are incorporated into a model, which employs linear mixing of volumes to determine the density of compositionally intermediate liquids in the CaO-MgO-Al₂O₃-SiO₂-FeO major element space. Liquid volumes are calculated for temperature and pressure conditions that are currently present at the core-mantle boundary or that may have occurred during differentiation of a fully molten mantle magma ocean.

The most significant implications of our results include: (1) a magma ocean of either chondrite or peridotite composition is less dense than its first crystallizing solid, which is not conducive to the formation of a basal mantle magma ocean, (2) the ambient mantle cannot produce a partial melt and an equilibrium residue sufficiently dense to form an ultralow velocity zone mush, and (3) due to the compositional dependence of Fe2+ coordination, there is a threshold of Fe concentration (molar X_Fe ≤ 0.06) permitted in a liquid for which its density can still be approximated by linear mixing of end-member volumes.

Selective hydroxylation of small alkanes by the particulate methane monooxygenase

The particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol under ambient temperatures and pressures. Other small alkanes and alkenes are also substrates of this enzyme. We measured and compared the initial rate constants of oxidation of small alkanes (C1 to C5) catalyzed by pMMO. Both primary and secondary alcohols were formed from oxidation of n-butane and n-pentane. The alcohols produced from alkane oxidation can be further oxidized, probably by pMMO, to aldehydes and ketones. The apparent regioselectivity for n-butane and n-pentane is 100% 2-alcohols because the formation of primary alcohols is slower than further oxidation of these alcohols. The hydroxylation at the secondary carbons is highly stereoselective: (R)-alcohols are preferentially formed. The enantiomeric excess increases slightly with decreasing reaction temperature. The steric course of hydroxylation on primary carbons was also studied by using isotopically substituted ethane: (S)- or (R)-CH_3-CHDT, and (S)- or (R)-CD_3- CHDT and the reactions were found to proceed with 100% retention of configuration. A primary isotopic effect of k_H/k_D=5.0 was observed in these experiments.

Exploiting seismic waveforms of ambient noise and earthquakes

In this thesis, I apply detailed waveform modeling to study noise correlations in different environments, and earthquake waveforms for source parameters and velocity structure.

Green's functions from ambient noise correlations have primarily been used for travel-time measurement. In Part I of this thesis, by detailed waveform modeling of noise correlation functions, I retrieve both surface waves and crustal body waves from noise, and use them in improving earthquake centroid locations and regional crustal structures. I also present examples in which the noise correlations do not yield Green's functions, yet the results are still interesting and useful after case-by-case analyses, including non-uniform distribution of noise sources, spurious velocity changes, and noise correlations on the Amery Ice Shelf.

In Part II of this thesis, I study teleseismic body waves of earthquakes for source parameters or near-source structure. With the dense modern global network and improved methodologies, I obtain high-resolution earthquake locations, focal mechanisms and rupture processes, which provide critical insights to earthquake faulting processes in shallow and deep parts of subduction zones. Waveform modeling of relatively simple subduction zone events also displays new constraints on the structure of subducted slabs.

In summary, behind my approaches to the relatively independent problems, the philosophy is to bring observational insights from seismic waveforms in critical and simple ways.

Techniques for strength measurement at high pressures and strain-rates using transverse waves

The study of the strength of a material is relevant to a variety of applications including automobile collisions, armor penetration and inertial confinement fusion. Although dynamic behavior of materials at high pressures and strain-rates has been studied extensively using plate impact experiments, the results provide measurements in one direction only. Material behavior that is dependent on strength is unaccounted for. The research in this study proposes two novel configurations to mitigate this problem.

The first configuration introduced is the oblique wedge experiment, which is comprised of a driver material, an angled target of interest and a backing material used to measure in-situ velocities. Upon impact, a shock wave is generated in the driver material. As the shock encounters the angled target, it is reflected back into the driver and transmitted into the target. Due to the angle of obliquity of the incident wave, a transverse wave is generated that allows the target to be subjected to shear while being compressed by the initial longitudinal shock such that the material does not slip. Using numerical simulations, this study shows that a variety of oblique wedge configurations can be used to study the shear response of materials and this can be extended to strength measurement as well. Experiments were performed on an oblique wedge setup with a copper impactor, polymethylmethacrylate driver, aluminum 6061-t6 target, and a lithium fluoride window. Particle velocities were measured using laser interferometry and results agree well with the simulations.

The second novel configuration is the y-cut quartz sandwich design, which uses the anisotropic properties of y-cut quartz to generate a shear wave that is transmitted into a thin sample. By using an anvil material to back the thin sample, particle velocities measured at the rear surface of the backing plate can be implemented to calculate the shear stress in the material and subsequently the strength. Numerical simulations were conducted to show that this configuration has the ability to measure the strength for a variety of materials.

Studies of ambient organic and inorganic aerosol in Southern California

The negative impacts of ambient aerosol particles, or particulate matter (PM), on human health and climate are well recognized. However, owing to the complexity of aerosol particle formation and chemical evolution, emissions control strategies remain difficult to develop in a cost effective manner. In this work, three studies are presented to address several key issues currently stymieing California's efforts to continue improving its air quality.

Gas-phase organic mass (GPOM) and CO emission factors are used in conjunction with measured enhancements in oxygenated organic aerosol (OOA) relative to CO to quantify the significant lack of closure between expected and observed organic aerosol concentrations attributable to fossil-fuel emissions. Two possible conclusions emerge from the analysis to yield consistency with the ambient organic data: (1) vehicular emissions are not a dominant source of anthropogenic fossil SOA in the Los Angeles Basin, or (2) the ambient SOA mass yields used to determine the SOA formation potential of vehicular emissions are substantially higher than those derived from laboratory chamber studies. Additional laboratory chamber studies confirm that, owing to vapor-phase wall loss, the SOA mass yields currently used in virtually all 3D chemical transport models are biased low by as much as a factor of 4. Furthermore, predictions from the Statistical Oxidation Model suggest that this bias could be as high as a factor of 8 if the influence of the chamber walls could be removed entirely.

Once vapor-phase wall loss has been accounted for in a new suite of laboratory chamber experiments, the SOA parameterizations within atmospheric chemical transport models should also be updated. To address the numerical challenges of implementing the next generation of SOA models in atmospheric chemical transport models, a novel mathematical framework, termed the Moment Method, is designed and presented. Assessment of the Moment Method strengths and weaknesses provide valuable insight that can guide future development of SOA modules for atmospheric CTMs.

Finally, regional inorganic aerosol formation and evolution is investigated via detailed comparison of predictions from the Community Multiscale Air Quality (CMAQ version 4.7.1) model against a suite of airborne and ground-based meteorological measurements, gas- and aerosol-phase inorganic measurements, and black carbon (BC) measurements over Southern California during the CalNex field campaign in May/June 2010. Results suggests that continuing to target sulfur emissions with the hopes of reducing ambient PM concentrations may not the most effective strategy for Southern California. Instead, targeting dairy emissions is likely to be an effective strategy for substantially reducing ammonium nitrate concentrations in the eastern part of the Los Angeles Basin.

Strength of tantalum at high pressures through Richtmyer-Meshkov laser compression experiments and simulations

Strength at extreme pressures (>1 Mbar or 100 GPa) and high strain rates (106-108 s-1) of materials is not well characterized. The goal of the research outlined in this thesis is to study the strength of tantalum (Ta) at these conditions. The Omega Laser in the Laboratory for Laser Energetics in Rochester, New York is used to create such extreme conditions. Targets are designed with ripples or waves on the surface, and these samples are subjected to high pressures using Omega’s high energy laser beams. In these experiments, the observational parameter is the Richtmyer-Meshkov (RM) instability in the form of ripple growth on single-mode ripples. The experimental platform used for these experiments is the “ride-along” laser compression recovery experiments, which provide a way to recover the specimens having been subjected to high pressures. Six different experiments are performed on the Omega laser using single-mode tantalum targets at different laser energies. The energy indicates the amount of laser energy that impinges the target. For each target, values for growth factor are obtained by comparing the profile of ripples before and after the experiment. With increasing energy, the growth factor increased.

Engineering simulations are used to interpret and correlate the measurements of growth factor to a measure of strength. In order to validate the engineering constitutive model for tantalum, a series of simulations are performed using the code Eureka, based on the Optimal Transportation Meshfree (OTM) method. Two different configurations are studied in the simulations: RM instabilities in single and multimode ripples. Six different simulations are performed for the single ripple configuration of the RM instability experiment, with drives corresponding to laser energies used in the experiments. Each successive simulation is performed at higher drive energy, and it is observed that with increasing energy, the growth factor increases. Overall, there is favorable agreement between the data from the simulations and the experiments. The peak growth factors from the simulations and the experiments are within 10% agreement. For the multimode simulations, the goal is to assist in the design of the laser driven experiments using the Omega laser. A series of three-mode and four-mode patterns are simulated at various energies and the resulting growth of the RM instability is computed. Based on the results of the simulations, a configuration is selected for the multimode experiments. These simulations also serve as validation for the constitutive model and the material parameters for tantalum that are used in the simulations.

By designing samples with initial perturbations in the form of single-mode and multimode ripples and subjecting these samples to high pressures, the Richtmyer-Meshkov instability is investigated in both laser compression experiments and simulations. By correlating the growth of these ripples to measures of strength, a better understanding of the strength of tantalum at high pressures is achieved.