Syntheses of various octasubstituted open-shell (Ni(II), Pd(II) and Pt(II)) metallophthalocyanines and their metal-free analogues have been carried out. Spectroscopic characterizations, photophysical and photochemical studies were carried out to determine the effects of these metals on the molecules using the metal-free phthalocyanine analogues as benchmark. Metal-binding studies of few thio-derivatised phthalocyanines were done to increase the number of palladium metal on the phthalocyanine ligands and determine the effect of increasing number of this metal on phthalocyanine properties. Palladium (PdPc) and platinum phthalocyanines (PtPc) gave good triplet and singlet oxygen quantum yields making them suitable for further investigation in application as photosensitisers. Using 4-nitrophenol as model pollutant, photosensitization reactions were carried out under homogenous and heterogeneous conditions. The reactions were monitored using UV-vis spectroscopy. The MPcs were adsorbed on functionalized single wall carbon nanotube (SWCNT-COOH) to form heterogeneous photosensitizers with PtPc failing to adsorb on the SWCNT-COOH. Under the heterogeneous condition, all the PdPcs photosensitization kinetics was consistent with Langmuir-Hinshelwood reaction model. The best photosenstiser, β-palladium dodecylthio phthalocyanine was also deployed in sensitization of oxidation of 4-chlorophenol and pentachlorophenol under homogenous and heterogeneous conditions to establish the ability of the molecules to sensitize oxidation of wide range of phenolic pollutants. Identifications of the products of the reactions were conducted using gas chromatography and high pressure liquid chromatography (HPLC) hyphenated with mass analyzer (LC-MS). Mechanisms of all the reactions were investigated and all the complexes, in spite of reduced lifetime resulting from open-shell nature of the metals, sensitized the reactions through singlet oxygen mediated pathway. All the heterogeneous sensitisers were recyclable in the 4- nitrophenol oxidation but β-palladium dodecylthio phthalocyanine proved unrecyclable in the oxidation of pentachlorophenol.

Hexachlorobenzene (HCB) is a persistent organic pollutant that was primarily produced for use as a fungicide dating back to the 1940s. Worldwide emissions have declined steadily over the past forty years, but HCB is still produced as a by-product of a number of industrial processes and is still detected in remote locations around the globe. Many studies have been conducted to determine the toxic and biochemical effects of HCB, but it has been suggested that reported toxic and biochemical effects initially attributed to HCB exposure may have actually been elicited by contamination of HCB by polychlororinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (PCBs). This thesis investigates whether highly purified HCB (HCB-P; defined as HCB containing < 0.2 ppb of any PCDD, PCDF, or co-planar PCB congener [the detection limit of current analytical methods]) can induce cytochrome P4501A (CYP1A) in three avian species in vitro. Primary cultures of chicken (Gallus gallus domesticus), ring-necked pheasant (Phasianus colchicus) and Japanese quail (Corturnix japonica) embryo hepatocytes were used to compare the potencies of reagent-grade (RG-HCB), HCB-P and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as inducers of ethoxyresorufin O-deethylase (EROD) activity, CYP1A4 messenger ribonucleic acid (mRNA) and CYP1A5 mRNA. The potencies of two mono-ortho substituted PCBs, 2,3,3’,4,4’-pentachlorobiphenyl (PCB 105) and 2,3’,4,4’,5-pentachlorobiphenyl (PCB 118) were also assessed in chicken embryo hepatocytes using the same endpoints. All compounds induced EROD activity and up-regulated CYP1A4/5 mRNAs in the hepatocytes of each species. The potency of HCB relative to the potency of TCDD (ReP) was 0.0001, 0.001 and 0.01 in chicken, ring-necked pheasant and Japanese quail embryo hepatocytes, respectively. ECthreshold values were suggested to be more appropriate than EC50 values because ECthreshold values account for differences in maximal EROD and CYP1A4/5 mRNA levels that are observed with HCB exposure in avian embryo hepatocytes more so than EC50 values. Differences in species sensitivity to HCB were also assessed, and did not vary as greatly as the listed ReP values. The results presented herein suggest that HCB is capable of inducing effects downstream of activation of the aryl hydrocarbon receptor, and may warrant its inclusion in the World Health Organization’s toxic equivalency concept.

<p>A computer technique for the optimization of thermal waste destruction systems for various design modes, with emphasis on satisfying the air pollution limitations is discussed. The approach considers the incineration of wastes by addition of fuels to permit the thermal destruction of waste materials which are potential pollutants. The computer optimizing package developed utilizes a modified form of a NASA chemical equilibrium program, the Pasquill-Gifford gas diffusion equation and an optimization routine. </p><p>The method employed incorporates the mathematical modeling of elementary incineration systems, with consideration of the practical aspects of the problem. The final computer design and assessment package is flexible and is developed in a way that permits upgrading and modification for realistic systems. </p> / Thesis / Master of Engineering (ME)

Submitted in complete fulfillment for the Degree of Master of Technology: Biotechnology, Durban University of Technology, Durban, South Africa, 2014. / Among persistent organic pollutants, chlorobenzenes are some of the most frequently encountered compounds in aqueous systems. These compounds can enter the environment via natural and anthropogenic sources, and are ubiquitous due to their extensive use over the past several decades. Several chlorobenzene compounds, once in the environment, can biologically accumulate, and are reputed to be carcinogens and extremely hazardous to health. Several chlorobenzenes are listed as priority pollutants by the United States Environmental Protection Agency. Excessive exposure to these compounds affects the central nervous system, irritates skin and upper respiratory tract, hardens skin and leads to haematological disorders including anaemia. In spite of these harmful effects, chlorobenzenes are still used widely as process solvents and raw materials in the manufacture of pesticides, chlorinated phenols, lubricants, disinfectants, pigments and dyes. In the light of the above, it is imperative to monitor the levels of chlorinated benzenes in all types of surface waters, using low-cost but sensitive methods of preconcentration and detection. In this study, a simple and relatively cheap preconcentration method using direct immersion solid phase microextraction (DI-SPME) followed by gas chromatography equipped with a flame ionisation detector (GC-FID) was developed for the analysis of 7 chlorinated benzenes in dam water. Experimental parameters affecting the extraction efficiency of the selected chlorobenzenes, such as fibre type, sample size, rate of agitation, salting-out effect and extraction time, were optimised and applied to the Grootdraai Dam water samples. The optimised method comprises the use of a 100 µm polydimethylsiloxane (PDMS) fibre coating; 5 ml sample size; 700 revolutions per minute rate of agitation and an extraction time of 30 minutes. The calibration curves were linear with correlation coefficients ranging from 0.9957–0.9995 for a concentration range of 1–100 ng/ml. The respective limits of detection and quantification for each analyte was as follows: 1,3-dichlorobenzene, 0.02 and 0.2 ng/ml; 1,4-dichlorobenzene, 0.04 and 0.4 ng/ml; 1,2-dichlorobenzene, 0.02 and 0.2 ng/ml; 1,2,4-trichlorobenzene, 0.3 and 2.7 ng/ml; 1,2,4,5-tetrachlorobenzene, 0.09 and 0.9 ng/ml; 1,2,3,4-tetrachlorobenzene, 0.07 and 0.7 ng/ml; pentachlorobenzene, 0.07 and 0.7 ng/ml. Recoveries ranged from 83.6–107.2% with relative standard deviation of less than 9%, indicating that the method has good precision, is reliable and free of matrix interferences. Water samples collected from the Grootdraai Dam were analysed using the optimised conditions to assess the potential of the method for trace level screening and quantification of chlorobenzenes. The method proved to be efficient, as 1,3 dichlorobenzene, 1,4-dichlorobenzene and pentachlorobenzene were detected at concentrations of 0.4 ng/ml, 1.7 ng/ml and 1.4 ng/ml, respectively.

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Ultrapure water is becoming increasingly important to the semiconductor, pharmaceutical and power industries. Stricter industrial requirements concerning water purity can be realized from pilot scale research. Such a system was designed and operated to determine improved methods to characterize and remove organic contaminants in industrial scale ultrapure water systems. Theoretical modelling of the polishing loop was performed for variable order kinetics; intrinsic reaction parameters were developed, and are potentially scaleable to larger systems. Application of the population balance to the actions of process components on organic particle distributions generated novel oxidation and fragmentation parameters that are scaleable to larger systems. Optimization of bacterial growth media resulted in the increased detection of viable bacterial concentrations. A significant fraction of TOC in the polishing loop was found to exist as assimilable organic carbon; the action of process components, thought to remove contaminants, can generate bacteria nutrients from more complex organics. The situating of a polymeric filter before a UV unit resulted in increased removal of organic contaminants; reversing the sequence enhanced the removal of low molecular weight and low charge to mass ratio compounds. The combination of UV-185 and dissolved ozone resulted in synergistic removal of organic contaminants from ultrapure water. The invention of a novel catalytic filter designed to physically separate and then oxidize contaminants resulted in enhanced removal of organics from ultrapure water. A study of viruses in ultrapure water showed that UV-185 and ozone effectively removed viruses, yet ion exchange gave only two orders of magnitude removal in viable counts. This research may be used to augment present systems and/or design new systems. Continued research along the lines specified in this document will generate further understanding of ultrapure water and ultrapure water systems.

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