Ever since the first observations of diffuse ultraviolet radiation by Hayakawa et al. (1969) and Lillie & Witt (1976), there has been an effort to understand its distribution and its origin. Unfortunately, because of the difficulty of the observations and the faintness of the background, many of the early observations were conspicuous more by their disagreements than by the light they shed on the topic. The state of the observations and theories before 1990 have been reviewed by Bowyer (1991) and Henry (1991). There has been significant progress in more recent years, particularly in the far ultraviolet (< 1200˚A) where Murthy et al. (1999) and Murthy & Sahnow (2004) have used spectroscopic data from the Voyager and FUSE (Far Ultraviolet Spectroscopic Explorer) spacecraft, respectively, to trace the radiation field over many different locations in the sky. There have also been a number of observations at longer wavelengths, most recently by the SPEAR instrument (Ryu et al. 2008, and references therein), but no systematic study of the UV background. The Galaxy Evolution Explorer (GALEX) offers us the opportunity to extend coverage of the diffuse background to a significant fraction of the sky with a sensitivity of better than 100 photons cm−2 sr−1 s−1 ˚A−1 . In this work, we will report on one such observation, that of the nebulosity observed near M82 by Sandage (1976). These GALEX observations are the first to probe the diffuse UV background at a spatial resolution comparable to other surveys of dust emission, notably the IR. We obtain a quantitative estimate of the Airglow, the Zodiacal Light and the Extragalactic Background Radiation. We have modelled the data with our monte carlo scattering simulation program, and inferred an estimate of albedo and scattering phase function parameter of the dust in Sandage region. In this thesis the methods and results of these deductions are explained in detail.

Ce travail de thèse, essentiellement de nature expérimentale, s’inscrit dans le domaine de la physique moléculaire en phase gazeuse avec des applications en astrophysique. Il porte sur l’étude de la photoexcitation et de la relaxation de molécules de la famille des cyanopolyynes qui sont détectées dans plusieurs objets du milieu interstellaire (nuages moléculaires, comètes) et dans les atmosphères planétaires comme celle de Titan. Ces composés participent à la chimie du carbone dans ces milieux en interagissant avec le rayonnement interstellaire ou avec le flux solaire dans le domaine spectral de l’ultraviolet du vide (VUV). La structure électronique excitée de plusieurs cyanopolyynes neutres a été étudiée avec la spectroscopie d’absorption par transformée de Fourier. Ces expériences ont permis d’identifier les états de Rydberg et de mesurer la section efficace absolue de photoabsorption. Parmi les processus de relaxation ouverts suite à la photoexcitation VUV, les voies d’ionisation et d’ionisation dissociative ont été explorées de façon détaillée à l’aide du rayonnement synchrotron SOLEIL ou du rayonnement laser du Centre Laser de l'Université Paris-Sud. Des informations variées (potentiels d’ionisation vers les premiers états électroniques, fréquences vibrationnelles, couplages vibroniques, etc) ont été obtenues sur les cations de cyanopolyynes via l’utilisation de la spectroscopie de photoélectrons de seuil et de la spectroscopie de photoélectrons d’énergie cinétique nulle. Enfin, la détection par spectrométrie de masse des fragments cationiques issus de l’ionisation dissociative a permis de mesurer leur énergie d’apparition et de déterminer leur voie de formation à l’aide de calculs DFT menés par un collaborateur. / This PhD thesis presents essentially an experimental work dealing with gas-phase molecular physics with astrophysical applications. The goal of the PhD is the study of the photoexcitation and relaxation of cyanopolyyne molecules that have been detected in different interstellar objects (molecular clouds, comets), and in planetary atmospheres (e.g. Titan). These molecules contribute to the carbon chemistry of these media by interacting with the interstellar radiation or with the solar flux in the vacuum ultraviolet range (VUV). The excited electronic structure of neutral cyanopolyynes was studied by absorption spectroscopy with a VUV Fourier-transform spectrometer. These experiments allowed us to identify the Rydberg states, and to measure the absolute photoabsorption cross section.Among the different open relaxation processes following a VUV photoexcitation, ionisation and dissociative ionisation have been investigated in detail using SOLEIL synchrotron radiation or laser sources of Centre Laser de l’Université Paris-Sud. Data on the ionisation potentials toward the first electronic states, vibrational frequencies, vibronic couplings, etc. were obtained on cyanopolyyne cations with the use of threshold photoelectron spectroscopy and zero-kinetic-energy photelectron spectroscopy. Finally, cationic species created by dissociative ionisation of cyanopolyynes were detected by mass spectrometry. The threshold energies were measured and the formation channel of these fragments was determined with the help of DFT calculations performed by a collaborator.

Indiana University-Purdue University Indianapolis (IUPUI) / In the area of forensic chemistry, improved or new analysis methods are continually being investigated. One common and powerful technique used in forensic chemistry is wall-coated open-tubular column (WCOT) gas chromatography with electron ionization single quadrupole mass spectrometry (GC-MS). Improvements to and effectiveness of alternatives to this instrumental platform were explored in an array of parallel inquiries. The areas studied included the column for the chromatographic separation, the universal detection method employed, and the fragmentation method used to enhance molecular identification. Superfine-micropacked capillary (SFµPC) columns may provide an alternative to commercial packed GC columns and WCOT GC columns that combines the benefits of the larger sample capacity of packed columns and the benefits of the excellent separation capabilities and mass spectrometry (MS) flow rate compatibility of WCOT columns. SFµPC columns suffer from high inlet pressure requirements and prior reported work has required specialized instrumentation for their use. Fabrication of and chromatography with SFµPC GC columns was successfully achieved with typical GC-MS instrumentation and within the flow rate limit of a MS. Additionally, the use of higher viscosity carrier gasses was demonstrated to reduce the required inlet pressure for SFµPC GC columns. Recently, a new vacuum ultraviolet spectrometer (VUV) universal detector has been commercialized for GC. The ability of VUV detectors to acquire absorbance spectra from 125 nm to 430 nm poses a potential alternative to MS. As such, GC-VUV provides an exciting potential alternative approach to achieving excellent quantitative and qualitative analysis across a wide range of analytes. The performance of VUV and MS detectors for forensic analysis in terms of quantitative and qualitative analysis was compared. Analysis of alkylbenzenes in ignitable liquids was explored, which can be important evidence from suspected arson fires and are difficult to differentiate with MS. The VUV detector was found to have superior specificity and comparable sensitivity to the MS detector in scan mode. Addition of thermolysis (Th) as an orthogonal fragmentation pathway provides the opportunity to increase the differences between MS fragmentation patterns. Fragmentation has been widely established to aid in identification of molecules with MS by providing characteristic fragments at characteristic relative abundances. However, molecules with very similar structures do not result in sizable spectral differences in all cases with typical MS fragmentation techniques. A series of Th units were fabricated and integrated into GC-Th-MS instruments. Th-MS was conducted with the thermally labile nitrate esters across a range of instrumentation and thermal conditions.

The Polstar mission will provide for a space-borne 60cm telescope operating at UV wavelengths with spectropolarimetric capability capturing all four Stokes parameters (intensity, two linear polarization components, and circular polarization). Polstar’s capabilities are designed to meet its goal of determining how circumstellar gas flows alter massive stars' evolution, and finding the consequences for the stellar remnant population and the stirring and enrichment of the interstellar medium, by addressing four key science objectives. In addition, Polstar will determine drivers for the alignment of the smallest interstellar grains, and probe the dust, magnetic fields, and environments in the hot diffuse interstellar medium, including for the first time a direct measurement of the polarized and energized properties of intergalactic dust. Polstar will also characterize processes that lead to the assembly of exoplanetary systems and that affect exoplanetary atmospheres and habitability. Science driven design requirements include: access to ultraviolet bands: where hot massive stars are brightest and circumstellar opacity is highest; high spectral resolution: accessing diagnostics of circumstellar gas flows and stellar composition in the far-UV at 122-200nm, including the NV, SiIV, and CIV resonance doublets and other transitions such as NIV, AlIII, HeII, and CIII; polarimetry: accessing diagnostics of circumstellar magnetic field shape and strength when combined with high FUV spectral resolution and diagnostics of stellar rotation and distribution of circumstellar gas when combined with low near-UV spectral resolution; sufficient signal-to-noise ratios: ~103 for spectropolarimetric precisions of 0.1% per exposure; ~102 for detailed spectroscopic studies; ~10 for exploring dimmer sources; and cadence: ranging from 1-10 minutes for most wind variability studies, to hours for sampling rotational phase, to days or weeks for sampling orbital phase. The ISM and exoplanet science program will be enabled by these capabilities driven by the massive star science.

An automated continuous flow analysis for milk protein utilizing ultraviolet spectroscopy resulted in a correlation coefficient of 0.972 and a standard estimate of error of 0.082 percent protein when 30 samples were compared with the acid orange 12 dye binding method. Milk was solubilized in 95-105 volumes of acetic acid using the Technicon Auto Analyzer II and measured for absorbance at 274 nanometers. No deviation from the standard method due to mastitis and varying milk fat concentration was observed. A theoretical model indicated a possible standard estimate of error 0.059 percent protein due to inter- and intra-breed variation in milk protein fraction distribution. Potassium dichromate and other preservatives interfered with the results.

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No / With the general increase in the worldwide incidence of tuberculosis there is increasing interest in the use of upper room ultraviolet germicidal irradiation (UVGI) systems to disinfect air. A number of researchers have demonstrated experimentally the ability of such systems to inactivate airborne microorganisms. However, relatively little theoretical work has been done to explain the results observed and few models exist to describe the performance of upper room UVGI systems. This paper presents a new model, which can be used both to design such systems and to evaluate their germicidal effectiveness. A theoretical study is undertaken, which indicates that although upper room UVGI systems work well at lower ventilation rates, they are of limited benefit in highly ventilated applications. The paper also demonstrates and quantifies the relationship between inter-zonal air velocity and room ventilation rate. In particular, the paper shows that under steady-state conditions the number of passes made by bioaerosol particles through an upper room UV field is independent of the ventilation rate.

Alpine zooplankton are exposed to a variety of stressors in their natural environment including ultraviolet radiation. Physiological coping mechanisms such as the accumulation of photoprotective compounds provide these zooplankton protection from many of these stressors. Elevated levels of carotenoid compounds such as astaxanthin have been shown to help zooplankton survive longer when exposed to ultraviolet radiation presumably due to the strong antioxidant properties of carotenoid compounds. This antioxidant capacity is important because it may ameliorate natural and anthropogenic stressor-induced oxidative stress. While previous researchers have shown carotenoid compounds impart increased resistance to ultraviolet radiation in populations of zooplankton, little work has focused on the toxicological implications of PAH induced phototoxicity on zooplankton containing high levels of carotenoid compounds. This thesis discusses research studying the role that carotenoid compounds play in reducing PAH induced phototoxicity. By sampling different lakes at elevations ranging from 9,500' to 12,700' in the front range of the Colorado Rocky Mountains, copepod populations containing different levels of carotenoid compounds were obtained. These populations were then challenged with fluoranthene and ultraviolet radiation. Results discussed include differences in survival and levels of lipid peroxidation among populations exhibiting different levels of carotenoid compounds, and the toxicological and ecological implications of these results.

Published Article / Alicyclobacillus acidoterrestris is a non-pathogenic, spore-forming bacterium that can survive the commercial pasteurisation processes commonly used during fruit juice production. Surviving bacterial endospores germinate, grow and cause spoilage of high acid food products. Fruit juices can be treated using ultraviolet light (UV-C) with a wavelength of 254 nm, which has a germicidal effect against micro-organisms. In this study, A. acidoterrestris was inoculated into water, used wash water from a fruit processing plant and grape juice concentrate. Ultraviolet dosage levels (J L-1) of 0, 61, 122, 183, 244, 305 and 367 J L-1 were applied using a novel UV-C turbulent flow system. The UV treatment method was shown to reliably achieve in excess of a 4 log10 reduction (99.99%) per 0.5 kJ L-1 of UV-C dosage in all the liquids inoculated with A. acidoterrestris. The applied novel UV technology could serve as an alternative to thermal treatments of fruit juices for the inactivation of Alicyclobacillus spores as well as in the treatment of contaminated wash water used in fruit processing.

Thesis (MSc (Physics))--University of Stellenbosch, 2005. / A tunable vacuum ultra-violet (VUV) laser source was recently developed for VUV spectroscopy using state selective excitation and total fluorescence detection. The VUV laser source makes use of a four-wave mixing process to provide tunable VUV radiation for the electronic excitation of the molecules. The theory of four-wave mixing, with the emphasis on parameters that are important for our experimental setup to generate efficient tunable VUV radiation is discussed. The experimental setup, and in particular the metal vapor heat-pipe, which provides Mg vapor as the nonlinear medium, is described. New diagnostic equipment described in this work was added to the experimental setup. This equipment was characterized and utilized together with the existing setup. The additional diagnostic equipment introduced enabled us to measure the tunable VUV output of the source (using a VUV monochromator), making it possible to significantly improve the efficiency of the existing tunable VUV laser source.