No description available.

Recently a new x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has been developed that is bulk sensitive and free of saturation effects, which also provides a direct measure of total absorption coefficient. However, IPFY was originally formulated for smooth bulk samples, but XAS is often performed on rough samples. To test the applicability of IPFY on rough surfaces, a model is presented and the calculations based on this model are compared to the experimental results measured on NdGaO3. It is shown that the correspondence between calculated and experimental intensities of IPFY is sufficient to corroborate this model a means of estimating the maximum allowable surface roughness size and the optimal detection geometry.

Food production systems need to keep pace with the rising global population. Food from aquatic environments comes from both capture fisheries and aquaculture. Industrial fishing pressure has caused a global loss of more than 90% of large predatory fishes and 80% of the world’s fish stocks are reported as fully exploited or overexploited. Global finfish, shellfish and aquatic plant aquaculture has been steadily increasing to meet the global demand for seafood. In British Columbia, aquaculture is primarily marine, with salmon and shellfish accounting for the majority of species cultured. Although shellfish aquaculture accounts for significantly less production and value compared to salmon aquaculture, the amount of foreshore dedicated to farming shellfish is nearly half (44%) the total area utilized by all aquaculture in the Province. Introduced Pacific oysters (Crassostrea gigas) (74%) dominate shellfish aquaculture in British Columbia. Pacific oysters are known to be very efficient generalist filter feeders that can grow faster and larger than native species. Extensive aquaculture is a form of aquaculture, where farmed animals feed exclusively on naturally occurring food in the surrounding water column. The goal of this research was to determine if there was a measureable depletion of phytoplankton around shellfish farms along the west coast of Canada and the United States. Chlorophyll-a, a pigment found within phytoplankton, was used as a proxy for phytoplankton abundance for this study. In field season one, two bays were studied, one exposed to shellfish culture (Westcott Bay) and one not exposed to shellfish culture (Fisherman Bay). The concentration of chlorophyll-a was measured in each bay at three locations at two depths (0.5 and 3 meters) and at two tidal heights (high and low). Chlorophyll-a concentration was found to be related to either depth or tide, with location in a bay showing no difference in either of the bays studied. In addition to water column measurements, 100 Pacific oysters were placed at two locations within Westcott Bay Seafarm to test for local differences in oyster growth. The results from this experiment showed that Pacific oysters grown in the center of a shellfish farm were smaller than oyster grown at the farm’s periphery. Field season two tested for spatial patterns between chlorophyll-a concentration and proximity to a shellfish farm in three different bays (Westcott Bay, Trevenon Bay and Gorge Harbour). A measureable depletion footprint of chlorophyll-a concentration was detected in the two sheltered shallow bays tested (Westcott Bay and Gorge Harbour), whereas no depletion footprint was detected in the exposed, deep bay (Trevenon Bay). Tide height played a significant role in predicating chlorophyll-a concentration in all three of the bays studied. These results suggested that some areas may be more suitable for shellfish culture than others. Taken together, this research demonstrated a measureable gradient of phytoplankton in sheltered shallow bays exposed to shellfish culture with depletion closest to the farm site, as well as greater oyster growth at the periphery of shellfish farms where phytoplankton would be predictably in greater abundance. / Graduate

Laser Induced Fluorescence has been used to study rotational and vibrational energy disposal following gas phase photodissociations and reactions of small molecules. Three distinct systems have been studied. The rotational and vibrational distributions in the ground and first electronically excited states of the OH radical have been studied following the two and three photon dissociation of water using laser radiation of 266nm and 355nm wavelength respectively. The results have been compared to recent theoretical calculations and experimental investigations at different wavelengths in the same region of the spectrum. The rotational distribution in vibrational levels of the ground electronic state of the NO molecule following 355nm photodissociation of methyl nitrite have been studied and compared to recent experimental studies of the photodissociation of NO containing molecules. A statistical treatment allowed the vibrational distribution to be determined. A simple model is described which rationalises the process. Finally, the rotational distributions within vibrational levels of the ground electronic state of the CO molecule, produced via the gas phase reaction between oxygen atoms and the CS radical, are presented. The vibrational distribution resulting from this reaction is well established but, to date, there have been no reports of the rotational distribution. A proposal has been made to employ the system studied in a vacuum ultra violet laser. Some comments are made concerning this proposal.

Measurement of the intrinsic properties of processing plasmas is critically important in understanding discharges so that the optimum conditions can be achieved. Several different diagnostic methods have been developed and tested. A planar probe has been used to measure the ion flux and electron temperature in both inductively coupled and capacitively coupled plasma systems, at various pressures and applied powers, using the assumption that the electron energy distribution is a Maxwellian.</p> Frequency modulation spectroscopy (FMS) has been used to detect species in a plasma. It has been shown to be very effective, giving a significantly increased S/N ratio compared to both single pass absorption and low frequency mechanical modulation techniques. It has been used to measure excited argon atom concentrations, in both capacitively and inductively produced plasmas. The argon atom 4s[3/2]₁ level concentration was found to be between 2 x 10⁸ and 1 x 10¹¹ atom/cm³ and to generally increase with increasing applied power and to decrease with increasing total pressure. The temperature of the atoms was also measured and was found to be approximately 323 ± 17 K. A simple compact laser source at 308 nm has been produced from a frequency doubled cooled commercial diode laser. This has been used to detect the OH radical, by absorption, within the afterglow of a microwave discharge, produced either directly or chemically. Simple kinetic models have provided explanations of the variations in OH concentration with discharge conditions. A novel method, cavity laser induced fluorescence (CLIP), that combines the advantages of both laser induced fluorescence (LIF) and cavity ring down spectroscopy CRDS, has been shown to increase the sensitivity of a diagnostic system compared to absorption. This method could be used to follow concentration variations of a reaction in a single laser shot. Although such variation can be observed using LIF, it requires a calibration and a many laser shot experiment with a signal recorded at each time point. Whilst CRDS allows temporal information about the absolute concentrations of the species observed to be obtained, it is not as sensitive as LIF. By combining the two in CLIP, it may be possible to retain the sensitivity of LIF with the advantage of CRDS so that absolute and time varying concentrations can be obtained in a single pulsed laser shot. LIF and CRDS signals have been observed using the A ²?_u ? X ²S_g⁺ transition of the N₂⁺ ion. The lifetime of the A ²?_u state in the discharge was found to be sufficiently long for a time of flight experiment to be contemplated (an ion with a velocity of 10 kms^-1 on average would travel 5 mm before radiating). Although the preliminary tests for the time of flight experiment have shown that this method is not feasible with a pulsed laser, the basic cavity locking procedures required for an analogous continuous wave experiment have been successfully demonstrated. A frequency doubled diode laser source has been constructed and tested, with the eventual aim of detecting N₂⁺ via the B ²S_u ? X ²S_g⁺ electronic transition. This has been found to be insufficiently intense to be used for a proposed two dimensional velocity mapping experiment, but several strategies to improve its performance are suggested.

An Optima 3000 ICP-AES instrument was modified and the equipment necessary to carry out axial excitation atomic fluorescence was designed and constructed. Using this calibrated system, preliminary fluorescence experiments were not successful. As fluorescence is proportional to source intensity, it was considered that the excitation source, a hollow cathode lamp, may not have been sufficiently intense to produce fluorescence. A novel excitation source-driver system was designed and built in-house to operate HCLs, BDHCLs and LEDs with variable modulation frequencies and duty cycle capabilities. Studies investigating lamp response to changes in modulation frequency and duty cycle indicated that a lamp operated with a lower modulation frequency range (167 - 542 Hz) and higher duty cycles (30 - 50 %) should provide the preferred intense excitation conditions for the production of fluorescence in the ICP, When a Thermo Elemental PQ2 instrument was used, fluorescence was obtained immediately. Um'variate searches were used to optimise several plasma parameters, i.e. forward power; viewing height ALC; plasma, nebuliser and auxiliary gas flow rates. Once the optimum conditions had been determined, calibration curves were plotted for each of the elements studied (Ba, Li, Mg and Na). The calibration showed excellent linearity over five orders of magnitude (R? values ranged from 0.99995 to 1.0000) and the precision on each data point was better than 5 % RSD. Limits of detection were determined to be 27.6, 0.51, 0.43 and 0.20 ug 1* for Ba, L i , Mg and Na, respectively, which approached those reported in the literature for a commercial system. Vertical profiles of the plasma, using radial excitation, were obtained for Ba, Li , Mg and Na. Using the optimum conditions for Li and Na, vertical profiles of the plasma, using axial excitation with the more intense LEDs, were obtained. Both profiles showed that there was a relatively sharp optimum, with respect to fluorescence signal, as a function of viewing height ALC. The optimum viewing heights ALC obtained, for both radial and axial excitation fluorescence, were identical, suggesting that, irrespective of the excitation arrangement employed, only particular conditions produced in the plasma give the optimum conditions for fluorescence and that these are spatially dependent. Plasma diagnostics were performed in an attempt to explain why fluorescence was observed using the plasma produced by the Thermo Elemental but not by the Optima 3000 generator. At a viewing height of 50 mm ALC, Texc and Trot were 3080 and 2500 K for plasmas produced using the Thermo Elemental generator and 3600 and 2830 K for the Optima 3000 generator, respectively. Temperatures were calculated using the mean emission intensity at particular wavelengths. The intensities of the emitting species from the Thermo Elemental ICP were lower than those obtained from the Optima 3000 ICP for supposedly 'identical' conditions. If the number of excited species gives rise to lower emission intensities, then there must be more atoms in the lower/ground state from the plasma produced using the Thermo Elemental generator. This is of vital importance because for fluorescence to occur the fluorescence emission intensity will be dependent on the number available in the ground state for excitation {i.e. a relatively 'cool' plasma is required for fluorescence to occur). As very similar plasma operating conditions and the same concentration solutions were used in the fluorescence experiments performed using both the Optima 3000 and the Thermo Elemental ICPs, the differences observed in plasma performance may be attributed to efficiency of coupling of the generators used.

No description available.

The developments of immunoassay methods for the early stage diagnosis of tuberculosis (TB) are described. These went through two different routes, one through flow injection analysis (FIA), and the other using immunochromatography methodology. The design of a simple longwavelength fluorescence detector to serve the above purposes has also been described. The FIA immunoassay methods involve immobilising antibodies on to beads, either directly or through protein A based solid phases. The beads are then packed into a micro-column reactor for incorporation into the FIA system. In this case reactor-bound molecules are eluted from the system by a change of pH, thus limiting the available fluorophores to those that are reasonably fluorescent in acid solution. Sandwich (reagent excess) assays have been investigated. A couple of long wavelength (600-800) fluorophores have been studied. The bead injection option has also been investigated. The immunochromatographic method uses a lateral flow system and a sandwich (two-site) immunometric assay. Capture antibodies are immobilised on a coated membrane matrix at a pre-determined position and the antigen is analysed after binding to a fluorescence-labelled antibody. Both fluorescent latex preparations and conventional fluorescent labels have been used and compared. The strips are simply immersed in a small volume of sample to start the analysis. The chromatographic step is rapid and extremely simple. The fluorescence detector is fitted with a motor-driven sample holder to allow the length of the immunochromatographic strip to be scanned. The detector utilises a diode laser light source, optical filters in the emission beam and a miniaturised photomultiplier. It can be easily modified for the FIA, and can readily be adapted to operate from batteries, so is suitable for field use.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

Thesis (M.S.)--University of Nevada, Reno, 2007. / "August 2007." Includes bibliographical references (leaves 36-38). Online version available on the World Wide Web.