The stable isotope compositions (chlorine, oxygen, and hydrogen), major anion concentrations, and major/minor cation concentrations of 37 thermal (any spring water with temperature at least 6.5° C above mean ambient air temperature) and mineral springs from the Cascade volcanic arc system were measured in order to better determine chlorine sources within the Cascades hydrothermal systems, and thus place better constraints on halogen flux through the subduction zone. Typically, most subduction zone flux calculations have been limited to the study of the erupted magmas and gases from fumarole vents, yet magmatic discharge through thermal springs may be considerable, particularly those in the often ignored forearc. Additionally, 9 geochemically well characterized lavas from across the Mt. St. Helens/Mt. Adams region of the Cascade arc (Leeman et al. 2001, 2005) were analyzed for their halogen concentrations, as well as their Cl stable isotope composition. Cl concentrations in the thermal springs range from 6 to 13,850 ppm and have δ37Cl values that range from -0.1‰ to + 1.9‰ (average = +0.8 ± 0.4‰; error = ± 0.2‰), with no systematic variation along or across the arc. The slightly positive values (~0.0 to +0.9‰) may be explained by fluid-rock interaction with underlying lithologic units, such as 37Cl-enriched volcanic sequences, and/or serpentinites or oceanic crust of accreted oceanic terranes. Another process possibly contributing to these positive δ37Cl values, particularly those with δ37Cl > 1‰, is magmatic HCl fractionation during degassing generating an enriched 37Cl vapor which mixes with thermal waters. We cannot completely rule out slab-derived altered oceanic crustal chlorine that has degassed into the springs, although most slab Cl is believed to have already been devolatilized from the slab before reaching sub-arc depths corresponding to longitudes where these springs are located at the surface. Lavas from the Columbia transect across the arc exhibit highest Cl concentrations at the volcanic front compared to the forearc and backarc. Br, like Cl, exhibits highest concentrations along the volcanic front. F and I show a progressive decrease in concentration from forearc to backarc which may demonstrate the putative early surge of fluids/fluid mobile element loss early in subduction at relatively shallow depth. δ37Cl values range from -0.1 to +0.8‰ (error = ± 0.2‰) and may reflect a component of assimilation of crustal material, or is derived from an enriched mantle, although we cannot completely rule out some isotopic fractionation and/or slab-derived chlorine. / text

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The long term degradation of polyethersulfone (PES) based ultrafiltration membranes used in the dairy industry has been investigated. The main aim of the study was to identify characterisation techniques which could give an indication of the condition and performance of ultrafiltration membranes after long term exposure to sodium hypochlorite solution. Membranes were degraded using sodium hypochlorite solution at pH 9, 10, 11 and 12, and with 5000 ppm-days to 25,000 ppm-days of exposure at 55°C. The degraded membranes were studied using the following characterisation techniques: dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), tensile testing, field emission scanning electron microscopy with energy dispersive x-ray spectroscopy (FESEM-EDS), Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), contact angle, drop absorption, zeta potential, liquid-liquid displacement porosimetery (LLDP), protein separation, and colour measurement. The protein separation test included membrane throughput measurements (using casein-whey as feed), with size exclusion chromatography and gel electrophoresis to analyse the feed, permeate and retentate. Also a membrane disinfection experiment was performed to study the effect of sodium hypochlorite pH on disinfection of mixed dairy culture.

The chemistry of stratospheric ozone is discussed and particular consideration is given to the role of chlorine compounds and to the impact of human activity on the ozone layer. An account is given of the methods used by other researchers to measure hydrogen chloride (HC1) in the stratosphere and their results are summarized. The pressure modulator radiometer (PMR) is an instrument which can be used to make remote measurements of atmospheric temperature and composition by sensing the radiation transmitted by or emitted from an atmospheric path containing gases with absorption bands in the infra-red. A balloon-borne PMR has been used to detect the absorption of solar radiation by the fundamental vibration-rotation band of HC1 at 3.5 micrometres. Using a limb scanning technique, the mixing ratio profile of HC1 has been measured over the height range, 16 to 39 km. It is shown that the amount of HC1 in an atmospheric path can be related to the PMR signals using a line-by-line method. The theory is developed in sufficiently general terms for it to be applicable to line-by-line calculations for many other gases with absorption bands in the infra-red. Consideration is given to the modelling of PMR measurements of transmission and emission both in the atmosphere and in the laboratory. The instrument used to measure HC1 is described in detail. The problems associated with the interpretation of the signals are discussed and an account of the instrument's laboratory testing is given. The reduction of the balloon flight data is described and the method used to retrieve the mixing ratio profile from the PMR signals is presented.

This thesis presents a study of antioxidant depletion in water containing chlorinated species (water containing 10 ppm either Cl2 or ClO2, buffered to pH = 6.8), the degradation products in the aqueous phase, and polyethylene pipe degradation scenarios. A low molecular weight hydrocarbon analogue (squalane) was used instead of solid polyethylene as the host material for the antioxidants, and the depletion of antioxidants has been studied. The phenolic antioxidant Irganox 1010 was consumed ca. 4 times faster in water containing 10 ppm ClO2 than in water containing 10 ppm Cl2. The different degradation products in extracts from the aqueous phase identified by infrared, liquid chromatography and mass spectrometry revealed the different degradation mechanisms between ClO2 (" cleavage) and Cl2 (hydrogen substitution). The squalane test shows no energy barrier between 30 and 70 °C, and the activation energy of the antioxidant in solid PE was found to be ca. 21 kJ mol-1. A linear relationship has been established between the time to reach antioxidant depletion in the polyethylene tape samples and the time to reach depletion in samples based on squalane containing the same antioxidants. The surface oxidation and surface embrittlement of PE tape on long time exposure have been studied by IR and SEM. Pressure testing on medium density PE pipes with a controlled pH aqueous media (6.8 ± 0.2) containing 4 ppm either ClO2 or at 90 °C showed that the stabilizers were rapidly consumed towards the inner pipe wall and the rate of consumption in ClO2 was 4 times greater than in Cl2 solution. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that, in the surface layer which came into contact with the oxidizing medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. / <p>QC 20130122</p>

xxi, 215 leaves : photos, graphs, tables ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Agricultural Biochemistry, 1979

Thesis (Ph. D.)--University of Washington, 2006. / Includes bibliographical references (leaves 157-161).