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No description available.

An investigation into the potential of time-wavelength resolved luminescence spectroscopy for the analysis of inorganic powders was performed. A time-wavelength resolved luminescence spectrometer consisting of an excimer laser, scanning monochromator, and gated integrator was constructed. The spectrometer had wavelength coverage from 265 nm to 800 nm, it was capable of measuring lifetimes between 100 ns and 500 ms. Sample excitation was done at 193 nm and 248 nm. A luminescence system model of first order decay in the time domain and a Gaussian function for the emission band was assumed. The time-wavelength resolved luminescence spectrum was described by the parameters: lifetime, peak maxima, peak halfwidth, and intensity factor. Parameter estimation was done with an algorithm employing a linear algebra construct and simplex optimization. The algorithm's performance on highly overlapped spectra was evaluated. For two component mixtures having a 1 % RSD noise level, overlaps greater than 0.3 halfwidths in the spectral domain and lifetime ratios greater than 1:1.3 were resolved with all parameter estimates having an error of less than ±2%. The luminescence spectra of CaMo0₄, SrMo0₄, BaMo0₄, ZnMoO₄, CdMo0₄, PbMoO₄, CaWO₄, SrW0₄, BaWO₄, ZnWO₄, CdW0₄ and PbWO₄ consisted of broad featureless bands showing simple exponential decay. Mixed crystals of Ca(MOxW₁-x)O₄ and Sr(MOxW₁-x)0₄ were examined. Tungstate emission was quenched by molybdate, the molybdate emission dominated when x was greater than 0.15. The tungstate lifetime was found to be proportional to molybdate concentration. The luminescence spectra of CaZrO₃, SrZr O₃, BaZr O₃ CaHfO₃ SrHfO₃, BaHfO₃, CaO, SrO, and BaO as pure compounds and doped with T1, Pb, Sb, and Bi were studied. The pure zirconates and hafnates showed short lived (<100 ns) luminescence with 248 not excitation; no readily discernible luminescence was observed with 193 nm excitation. Doped compounds tended to show luminescence characteristic of the dopant ion. / Science, Faculty of / Chemistry, Department of / Graduate

Thesis (M. Phil.)--University of Hong Kong, 2002. / Includes bibliographical references (leaves 58-61).

Thesis (Ph.D.) - University of Glasgow, 2007. / Ph.D. thesis submitted to the Department of Geographical & Earth Sciences, University of Glasgow, 2007. Includes bibliographical references. Print version also available.

Thesis (doctoral)--Universität zu Tübingen, 1982. / Vita. Includes bibliographical references (p. 85-87).

Thesis (Ph.D.) - University of St Andrews, April 2009. / Restricted until 20th April 2010.

published_or_final_version / Physics / Master / Master of Philosophy

The research described in this dissertation is the first evaluation and application of a new class of optical detectors, two-dimensional charge-coupled device (CCD), for low-light level chemiluminescence and other luminescence spectroscopies. This research conclusively demonstrates the superior qualitative and quantitative performance of spectrometric systems which employ these detectors. It is experimentally shown that a single detector element of a CCD has comparable or superior sensitivity to the most sensitive single channel detectors; photomultiplier tubes (PMT). The results from the application of the CCD detector system to molecular spectroscopies (fluorescence, chemiluminescence, fluorescence detection of high performance liquid chromatography (HPLC) effluents, and chemiluminescence detection of HPLC effluents) and atomic spectroscopies (spatially and spectrally resolved spark and direct current plasma are presented). The results of operating the CCD in specialized readout modes developed in this research termed charge dependent variable binning (CDVB), simultaneous variable binning (SVB), and continuous high speed spectral framing (CHSF) are described and applied. The CDVB and SVB techniques allow very sensitive quantitation of spectrally resolved and unresolved signals with very wide dynamic ranges without prior knowledge of the signal intensity. Finally, CHSF technique provides spectrally resolved temporal study of extended period luminescence emission with millisecond time resolution. The results of unique algorithms to restore the integrity of the image obtained with a two-dimensional CCD detector are described and applied. The algorithms implemented are for removing variations in detector sensitivity and responsivity and spectrometer efficiency, as well as providing digital image filtering.

The immobilisation of uranium is an important issue within the nuclear industry due to contaminated land from accidental spillage, weapons testing or mining activities. Within the environment uranium is most commonly found in the +VI oxidation state as the mobile uranyl cation [UO2]2+. Alternatively, the +IV oxidation state can also be found in the environment, forming either an insoluble crystalline uraninite phase, or a more soluble molecular uranium(IV) species. Many endogenous subsurface bacteria can bind and accumulate actinide ions through biosorption and can reduce mobile uranyl(VI) species down to immobile uranium(IV) compounds and mineral phases. This work presents an investigation into the bioreduction process by two anaerobic Gram-negative bacteria, Geobacter sulfurreducens and Shewanella oneidensis MR-1. Luminescence spectroscopy is used to monitor the intensity of uranyl(VI) emission in situ over the course of a 24 hour bioreduction experiment with uranyl(VI) acetate as the electron acceptor and either acetate or lactate as the electron donor. An increase in intensity of the emission around hour three or four during the reduction, followed by an overall decrease, is attributed as the disproportionation of an unstable uranyl(V) intermediate. The role of inner and outer membrane c-typecytochromes as well as flavin secretion is also investigated using three deletion mutants of the S. oneidensis bacteria, which shows that in their absence, the reduction of uranyl(VI) does not occur over the course of 24 hours. The emission of uranium(IV) is also investigated during bioreduction in phosphate media and results show that emission can be observed in aqueous solutions at pH 7 pointing to the presence of a molecular product. One photon confocal and two photon fluorescence microscopy has been utilised for the very first time to directly optically image the bioreduction of uranyl(VI) in combination with luminescence lifetime mapping. The sorption of uranyl(VI) onto the surface of the bacteria with differing lifetimes indicates a direct interaction between uranyl(VI) and surface bound c-type cytochromes, since this variation was not observed in mutant S. oneidensis strains where the cytochromes were not present. Combined, these results have established the applicability of optical spectroscopy and microscopyin tracking the bioreduction of uranium in situ.