The kinetics of Escherichia coli inactivation were studied using ultraviolet (UV) radiation, ozone, and UV and ozone (UVO) in combination in a batch reactor at varying pH levels (6, 7, and 8) and at a constant temperature of 25°C. The inactivation kinetics for all three treatment processes was pseudo first order, and the reaction rate constants were considered to be additive such that a combined reaction rate could be obtained by adding the kinetic rates of the processes applied and numerically small rates could be neglected in the computation of the combined rate. Statistical tests (ANOVA and student's t-test) performed on the inactivation data indicated no apparent effect of pH on the kinetics of the processes. It was found that the UVO process was the most efficient in inactivating E. coli. The increase in the inactivation rate with the UVO process is attributed to synergetic activity of UV and ozone which results in the generation of hydroxyl radicals from ozone decomposition.

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No / A new technique using ozone loaded on adsorbents for industrial waste-water treatment has been investigated. This is a three-step process: ozone adsorption on a fixed bed column; water treatment on the bed loaded with ozone; and finally drying/ regeneration of the wet bed. Silica gel of mean particle size of 1.5 mm has been tested for ozone loading capacities followed by water treatment, both at ambient temperature. The mechanisms of the mass transfer process during ozone loading and water treatment have been established. The drying of the adsorbent using vacuum and dry air is feasible, but it is a time-consuming operation. A design procedure is described for the whole system.

No / Extracting waterborne contaminants to ozone-loaded Volasil¿245 (a siloxane solvent in which ozone is ten times more soluble than water) has been studied as a means of enhancing reaction kinetics and thus, providing more rapid wastewater decontamination. Investigation was carried out with respect to 2-chlorophenol and dichloromethane. Using a pilot scale continuous flow liquid¿liquid/ozone water treatment system, 2-chlorophenol was extracted to the ozone-loaded solvent phase and considerable extents of destruction were achieved. However, the approach was demonstrated to yield slightly less destruction than direct gas contact for the same utilization of ozone and enhanced reaction kinetics were not shown to occur. This was suggested to be due to increased interfacial mass transfer resistance and/or the promotion of less destructive reaction pathways. Modification of the existing pilot system, by conversion from co- to counter-current solvent-loading, enabled greater dissolved ozone concentrations to be achieved within the solvent. Increasing the counter-current exchange column height to not, vert, similar2.5 m was suggested for achieving a near optimum level of performance. The liquid¿liquid/ozone approach was demonstrated to be an effective means of indirectly exposing wastewater contaminants to concentrated ozone. As such the technology may be applicable as an alternative to direct gas contact in instances where the avoidance of contaminant sparging is desired (i.e. where contaminants are highly volatile, pungent and/or toxic) or foaming occurs

No / In the search for an efficient and economical method to treat a leachate generated from a controlled municipal solid waste landfill site (Jebel Chakir) in the region of greater Tunis in Tunisia, ozone alone and ozone combined with hydrogen peroxide were studied. The leachate was characterised by high COD, low biodegradability and intense dark colour. A purpose-built reactor, to avoid foaming, was used for the study. It was found that ozone efficacy was almost doubled when combined with hydrogen peroxide at 2 g/L but higher H2O2 concentrations gave lower performances. Enhancement in the leachate biodegradability from about 0.1 to about 0.7 was achieved by the O3/H2O2 system. Insignificant changes in pH that may due to buffering effect of bicarbonate was found. A small decrease in sulphate concentrations were also observed. In contrast, chloride concentration declined at the beginning of the experiment then increased to reach its initial value. Estimates of the operating costs were made for comparison purposes and it was found that the O3/H2O2 system at 2 g/L H2O2 gave the lowest cost of about 3.1 TND (2.3 USD)/kg COD removed.

This dissertation describes the current and common problem of removing low concentrations of pollutants known as volatile organic compounds (VOCs) from large volume gas emissions. Silica-supported manganese oxide catalysts with loadings of 3, 10, 15, and 20 wt. % (as MnO2) were characterized using x-ray absorption spectroscopy and x-ray diffraction (XRD). The edge positions in the x-ray absorption spectra indicated that the oxidation state for the manganese decreased with increasing metal oxide loading from a value close to that of Mn2O3 (+3) to a value approximating that of Mn3O4 (+2⅔). The XRD was consistent with these results as the diffractograms for the supported catalysts of higher manganese oxide loading matched those of a Mn3O4 reference. The reactivity of the silica-supported manganese oxide catalysts in acetone oxidation using ozone as an oxidant was studied over the temperature range of 300 to 600 K. Both oxygen and ozone produced mainly CO₂ as the product of oxidation, but in the case of ozone the reaction temperature and activation energy were significantly reduced. The effect of metal oxide loading was investigated, and the activity for acetone oxidation was greater for a 10 wt. % MnOx/SiO2 catalyst sample compared to a 3 wt. % MnOx/SiO2 sample. A detailed mechanistic study of acetone oxidation using ozone was performed on a 10 wt. % silica-supported manganese oxide catalyst utilizing Raman spectroscopy, temperature programmed desorption (TPD), and kinetic measurements. In situ Raman spectroscopy at reaction conditions identified a band at 2930 cm-1 due to an adsorbed acetone species on the silica support and a band at 890 cm-1 due to an adsorbed peroxide species on the manganese oxide. A steady-state kinetic analysis, which varied acetone partial pressure (101 – 405 Pa), ozone partial pressure (101 – 1013 Pa), and temperature (318, 333, 343, and 373 K), was used to determine reaction rate expressions, while a transient kinetic study (318 K) was used to determine the role of the adsorbed species in the reaction mechanism. It was found that the rates of the acetone and ozone reactions were equally well described by both a power rate law and a Langmuir-Hinshelwood expression. The transient experiments showed that the rates of formation and reaction of the observed peroxide surface species did not correspond to the overall reaction rate, and it was concluded that it was not directly involved in the rate determining step of the reaction. A mechanism is proposed involving the reaction of an adsorbed acetone intermediate with an atomically adsorbed oxygen species via a dual site surface reaction to form complete oxidation products. / Ph. D.

Soybean cultivars (Glycine max (L.) Merr.), "Dare", "Williams" and "Essex", with differential sensitivity to ozone (O₃) based on visible injury were exposed once to 0.20 µl⁻¹ O₃ and/or 0.70 µl 1⁻¹ sulfur dioxide (SO₂) for 4 hr. The cv Dare was considered sensitive, cv Williams intermediate and cv Essex tolerant to O₃. Cultivars exposed to filtered air served as controls. Gas exchange measurements were conducted and antioxidant metabolites (reduced and oxidized glutathione: GSH, GSSG; reduced and oxidized ascorbate: AA, dHAA) concentrations and enzymes (glutathione reductase: GRase; ascorbate peroxidase: APase; superoxide dismutase: SOD) activities were analyzed. Gas exchange rates of all cultivars were significantly inhibited by pollutants exposure. The cv Essex maintained significantly higher net photosynthesis (Pn) at the end of 03 exposure, during the SO₂ exposure and in the first 2 hr of O₃/SO₂ fumigation. During O₃/SO₂ exposure, the estimated pollutant fluxes were 50% and integrated doses were 25-30% of O₃ or SO₂ when fumigated singly. During O₃ fumigation, cv Dare exhibited a higher O₃ flux and integrated O₃ dose. However, cv Essex showed a higher O₃/SO₂ peak flux in O₃/SO₂ fumigation. The cv Williams showed the lowest pollutant flux in all treatments. Ozone fumigation imposed a substantial, but statistically insignificant, effect on some antioxidant components. Relative to the controls, O₃ exposure resulted in increases of GRase and SOD activity in cv Dare. In cv Williams, decreases of GSSG and SOD total activity and increase of dHAA were observed. Decreases of AA and SOD activity and increases of GSSG, dHAA and APase activity in cv Essex were found. The SO₂ exposure resulted in increases of glutathione, particularly GSSG, in all cultivars. The cv Dare responded with increases in AA, APase specific activity and SOD activity. In cv Williams, AA and SOD specific: activity increased and APase activity decreased. Decline of SOD activity in cv Essex was found after SO₂ exposure. The O₃/SO₂ fumigation resulted in increases of glutathione, particularly GSSG, and GRase activity, in all cultivars. Declines of dHAA and SOD activity in cv Williams were found. The cv Essex responded with a decline of AA and increases of dHAA and specific activity of APase and SOD. Ozone and SO₂, singly or in combination, inhibited gas exchange rates in all cultivars, however, cv Essex was the least affected. Stomatal conductance was inhibited greater by O₃ than by SO₂ fumigation. Conversely, Pn was suppressed more by SO₂ than by O₃. The O₃/SO₂ fumigation, however, suppressed Pn and Cs substantially and to a greater extent than individual pollutants. Under the pollutant dose and fumigation profile used in these studies, no consistent responses of different antioxidant components to O₃ and/or SO₂ correlated with differential sensitivity of these soybean cultivars as determined from foliar symptomology. / Ph. D.

Understanding and establishing reaction mechanisms is an important area in heterogeneous catalysis. This dissertation describes the use of in situ laser Raman spectroscopy combined with kinetic measurements and dynamic experiments to determine the mechanism of catalytic reactions. Two cases involving ozone reactions on manganese oxide catalysts were treated. Manganese oxide was chosen because it is the most active of the transition metal oxides for ozone decomposition and because it is a well-known catalyst for complete oxidation reactions. The first case studied was that of the ozone decomposition reaction on a supported manganese oxide catalyst. An adsorbed species with a Raman signal at 884 cm-1 was observed and assigned to a peroxide species based on results of in situ Raman spectroscopy, 18O isotopic substitution measurements, and ab initio MO calculations. The reaction pathway of ozone decomposition was elucidated with carefully designed isotopic experiments. The reaction sequence was found to involve two irreversible, kinetically significant steps: 1) dissociative adsorption of ozone to form a peroxide species and an atomic oxygen species, and 2) desorption of the peroxide intermediate. The kinetic behavior of the peroxide species and the overall decomposition reaction were investigated to test the validity of the proposed sequence. The transient kinetics were found to be consistent with the steady state kinetics, and both were well represented by the two-step sequence, indicating that the proposed reaction sequence accurately described the mechanism of decomposition. The surface was found to be non-uniform, with activation energies that varied linearly with coverage. At zero surface coverage the activation energy for ozone adsorption was found to be 6.2 kJ mol-1, while that for desorption of the peroxide species was found to be 69.0 kJ mol-1. The second case investigated was that of ethanol oxidation using ozone on alumina and silica supported manganese oxide catalysts. Ethanol was found to react with ozone at lower temperatures than with oxygen, and also with a lower activation energy. The reaction kinetics was found to be well described by a power law equation with the reaction orders on ozone and ethanol being 0.89 and 0.81 respectively. The oxidation reactivity was found to be closely related to that of ozone decomposition, suggesting an important role of ozone decomposition in the reaction mechanism. In situ laser Raman spectroscopic studies showed the existence of adsorbed ethoxide species on the catalyst surface under reaction conditions, however, at a much lower concentration than when oxygen alone was used as the oxidant. Transient experiments provided direct evidence that surface peroxide (an adsorbed species due to ozone) and surface ethoxide (an adsorbed species due to ethanol) reacted with each other on the catalyst surface. / Ph. D.