Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

Water resources in South Africa are scarce, and should therefore be protected against pollutants, also from persistent organic pollutants (POPs). This is emphasised by the Stockholm Convention on POPs, which aims at reducing and ultimately eliminating POPs. South Africa signed and ratified the treaty, and it became international law on 17 May 2004. POPS are highly stable, toxic, hydrophobic and lipophilic compounds, with the ability to accumulate in biological tissues. Previous research had shown that dioxin-like POPS are present in the aquatic environments of South Africa, with the highest concentrations of these substances measured in industrialised areas of South Africa. The present study aimed at investigating the extent of polychlorinated dibenzo-para-dioxin (PCDD), polychlorinated dibenzo-furan (PCDF) and polychlorinated biphenyl (PCB) pollution in the Vaal Triangle, by targeting aquatic sediments and biota. Sediment samples were collected from the Blesbok Spruit, Taaibos Spruit, Leeu Spruit and Suikerbosrand River, and fish tissue samples were collected from Blesbok Spruit and Suikerbosrand River, to determine bio-accumulation. The samples were extracted with organic solvents, cleaned-up and fractionated. Raw extracts and fractions were analysed with the H4IIE-luc reporter gene bio-assay. This bio-assay is a rapid, sensitive and relatively cost-effective method, which measures the effects of dioxin-like compounds on rat hepatoma cells, transfected with firefly luciferase gene. Selected samples were analysed with gas chromatographylmass spectrometry (GCIMS) to confirm results. Only one site had quantifiable amounts of dioxin-like substances in the sediment, measured to be 52.35 ng/kg [Effective Concentration 50 (EC 50)]. This value exceeds many of the European and USA quality guidelines, proposed for sediments. No dioxin-like substances were found in fish tissues. The absence of PCDD/Fs and PCBs in aquatic sediments and fish tissues from the Vaal Triangle area might be due to the climatic conditions of the area, dilution effects in streams, and degradation of these compounds by UV-radiation and microbial organisms. / Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

Water resources in South Africa are scarce, and should therefore be protected against pollutants, also from persistent organic pollutants (POPs). This is emphasised by the Stockholm Convention on POPs, which aims at reducing and ultimately eliminating POPs. South Africa signed and ratified the treaty, and it became international law on 17 May 2004. POPS are highly stable, toxic, hydrophobic and lipophilic compounds, with the ability to accumulate in biological tissues. Previous research had shown that dioxin-like POPS are present in the aquatic environments of South Africa, with the highest concentrations of these substances measured in industrialised areas of South Africa. The present study aimed at investigating the extent of polychlorinated dibenzo-para-dioxin (PCDD), polychlorinated dibenzo-furan (PCDF) and polychlorinated biphenyl (PCB) pollution in the Vaal Triangle, by targeting aquatic sediments and biota. Sediment samples were collected from the Blesbok Spruit, Taaibos Spruit, Leeu Spruit and Suikerbosrand River, and fish tissue samples were collected from Blesbok Spruit and Suikerbosrand River, to determine bio-accumulation. The samples were extracted with organic solvents, cleaned-up and fractionated. Raw extracts and fractions were analysed with the H4IIE-luc reporter gene bio-assay. This bio-assay is a rapid, sensitive and relatively cost-effective method, which measures the effects of dioxin-like compounds on rat hepatoma cells, transfected with firefly luciferase gene. Selected samples were analysed with gas chromatographylmass spectrometry (GCIMS) to confirm results. Only one site had quantifiable amounts of dioxin-like substances in the sediment, measured to be 52.35 ng/kg [Effective Concentration 50 (EC 50)]. This value exceeds many of the European and USA quality guidelines, proposed for sediments. No dioxin-like substances were found in fish tissues. The absence of PCDD/Fs and PCBs in aquatic sediments and fish tissues from the Vaal Triangle area might be due to the climatic conditions of the area, dilution effects in streams, and degradation of these compounds by UV-radiation and microbial organisms. / Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

In the transition to a sustainable energy supply there is an increasing need to use biomass for replacement of fossil fuel. A key challenge is to utilize biomass conversion technologies in an environmentally sound manner. Important aspects are to minimize potential formation of persistent organic pollutants (POPs) such as dioxins and dioxin-like compounds. This thesis involves studies of formation characteristics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) in microwave-assisted pyrolysis (MAP) and torrefaction using biomass as feedstock. The research focuses are on their levels, distributions, fingerprints (homologue profiles and isomer patterns) and the underlying formation pathways. The study also included efforts to optimize methods for extracting chlorinated aromatic compounds from thermally treated biomass. The overall objective was to contribute better understanding on the formation of dioxins and dioxin-like compounds in low temperature thermal processes. The main findings include the following: Pressurized liquid extraction (PLE) is applicable for simultaneous extraction of PCDDs, PCDFs, PCNs, polychlorinated phenols and benzenes from thermally treated wood. The choice of solvent for PLE is critical, and the extraction efficiency depends on the degrees of biomass carbonization. In MAP experiments PCDDs, PCDFs and PCNs were predominantly found in pyrolysis oils, while in torrefaction experiments they were mainly retained in solid chars with minor fractions in volatiles. In both cases, highly chlorinated congeners with low volatility tended to retain on particles whereas the less chlorinated congeners tended to volatize into the gas phase. Isomer patterns of PCDDs, PCDFs and PCNs generated in MAP were more selective than those reported in combustion processes. The presence of isomers with low thermodynamic stability suggests that the pathway of POPs formation in MAP may be governed not only by thermodynamic stabilities but also by kinetic factors. Formation of PCDDs, PCDFs and PCNs depends not only on the chlorine contents in biomass but also the presence of metal catalysts and organic/metal-based preservatives. Overall, the results provide information on the formation characteristics of PCDDs, PCDFs and PCNs in MAP and torrefaction. The obtained knowledge is useful regarding management and utilization of thermally treated biomass with minimum environmental impact.

We take 5,6,11,12,17,18-hexaaztrinaphthylene and dibenzo[a,c]phenazine as our central core that with dove-tailed side chains. It is shown that the size-related increase of steric interactions among the peripheral side chains substituted to the aromatic core leads to a dramatically lowered isotropization temperature.

The characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and the variation of the gas-particle partitioning of PCDD/Fs near two municipal solid waste incinerators (MSWIs) located in southern Taiwan were investigated. In order to better understand the mechanism of dry deposition, the atmospheric dry deposition flux and velocity of PCDD/Fs were calculated. It was found that the mean atmospheric PCDD/F concentrations (0.0348-0.106 pg I-TEQ/Nm3) were comparable to those detected in the vicinity of MSWIs in Taiwan, but significantly lower than those in a highly industrialized urban area (0.150 pg I-TEQ/Nm3) located in southern Taiwan. The relatively higher atmospheric PCDD/F concentrations was found in winter than in summer. The calculated total dry deposition flux of PCDD/Fs ranged from 0.0274-0.718 ng I-TEQ/m2-month, and the atmospheric deposition flux in winter tended to be higher than those in summer. The results also indicated that dry deposition velocities of atmospheric particles for each month ranged from 0.52-0.91 cm/s (mean = 0.63 cm/s) and 0.48-0.73 cm/s (mean = 0.55 cm/s) in sites A and B, respectively, which were similar to that for the ambient air near two MSWIs in Taiwan, but slightly higher than those in urban area of Korea. In addition, the dry deposition of PCDD/Fs was mainly contributed by particle-phase at both sampling areas during the estimated period. The above results demonstrated that the dominant mechanism of dry deposition was particle phase deposition. The annual variations of wet deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in atmosphere were also measured at two sites (A and B). Results showed that particle scavenging dominates in the wet deposition processes for the removal of PCDD/Fs from the atmosphere, the highest value was observed at the highest chlorinated congener. The ambient temperature and the amount of precipitation played an important role in the variation of PCDD/F deposition fluxes. It was found that temperature was inversely associated with the existence of particulate PCDD/Fs, indicating PCDD/Fs are scavenged most efficiently in cold weather. PCDD/F wet deposition fluxes in rainy seasons (from June to August) were significantly higher than those in dry seasons (from December to February), revealing a positive relationship between wet deposition flux and monthly rainfall. Additionally, the annual total (dry + wet) deposition fluxes of PCDD/Fs were 149 ng/m2-year (5.02 ng I-TEQ/m2-year) and 177 ng/m2-year (5.11 ng I-TEQ/m2-year) for sites A and B, respectively, revealing that dry deposition was more dominant than the wet deposition for the atmospheric deposition of PCDD/Fs. Since atmospheric deposition is believed to be the main transfer pathway of PCDD/Fs into food chains, its impact on human exposure to PCDD/Fs is of great importance.

Gold catalysts have the characteristic of promoting nucleophilic reaction. The cyclization reaction of enediynes catalyzed by gold activated by silver in toluene at 100oC to give 6H-dibenzo[c,h]chromen-6-ones (63), 6H-benzo[c]chromen-6-one (66) and Arnottin I (10) is described. Treatment of enediynes (61¡B65) with 5 mol% of Ph3PAuCl and 10 mol% of AgSbF6 in toluene at 100oC gave 6H-dibenzo[c,h]chromen-6-ones (63) and 6H-benzo[c]chromen-6-one (66) in good yield. In addition to using gold catalyst, electrophilic reagents employed in the reaction caused one cyclization instead of two cyclization. Furthemore, a mechanistic study and GC-MS data showed that the toluene could participate in the reaction. Enediynes (73) can be synthesized by a series of organic synthesis with few steps. Treatment of enediynes (73) with 5 mol% of Ph3PAuCl and 10 mol% of AgSbF6 in toluene at 100oC gave natural product-Arnottin I (10).

The dibenzo[a,c]phenazine dimers with the branched alkoxy chain of disc were synthesized simplely. We now show on the synthesis of this series of compounds which were found to exhibit mesomorphism as determined by polarized optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). These materials showed polymeso- morphism and glass formation. In our investigations, we also observed that the effects of branched chains on dibenzo[a,c]phenazine enhanced columnar liquid crystal phase stability indeed.

In this PhD thesis, there are two major motifs: dibenzo[a,c]phenazine- and 2,3-diphenylquinoxaline novel discogens and fluorous polycatenar liquid crystals. The thermo properties of these new compounds were elucidated using optical microscopy, differential scanning calorimetry and powder X-ray diffraction. In the phenanthroline series (Chapter 2), 1,10-phenanthroline core incorporated into dibenzo[a,c]phenazine structure exhibit columnar mesophases with extremely wide width. X-ray diffraction study pinpoints to that half-shaped mesogens with reduced symmetry has preferential intra-molecular parallel conformation in the mesophase. This molecule has gel ability with different solvents. In dimeric crown ether series (Chapter 3A), 2,3-diphenylquinoxaline-based mesogens containing dibenzo-18-crown-6 has hexagonal columnar mesophase with extremely narrow width. Incorporation potassium metal ion into crown moiety dramatically enhanced mesomorphic stability and for metal complexes, as side chain increases, hexagonal mesophases predominate over rectangular mesophases. Furthermore, both in hexagon or rectangle, per columnar slice consist of two molecules. All of prolonged long glassy formation up to one year at room temperature. In monomeric crown ether series (Chapter 3B), metal-free molecules fail to be mesomorphic, but complexation with lithium and sodium metals enhanced thermo stability and rectangular mesophase (C2mm) were found. Also, per columnar slice was comprised of four molecules. Last (Chapter 4), a series of tri- and tetra-catenar mesogens containing various combinations of hydrocarbon and semiperfluorocarbon chains has been prepared to elucidate the fluorophlic-fluorophobic effect on mesomorphism. Tricatenar with one terminal semiperfluoro- and two hydrocarbon chains are aligned into lamellar periodicity driven by the mutual incompatibility of the hydrocarbon and fluorocarbon portions. But unsymmetric tetracatenar mesogens show rectangular mesophase.

Discotic liquid crystals (DLC) have been reported with a large number of discoid cores to improve the degree of intermolecular ordering because the liquid crystals own to self-assembly into columnar stacking and self¡Vhealing ability. In my research, a series of disc-like £k-conjugated molecules based on aromatic rigid cores have been newly synthesized. I focus on the hexaazatrinaphthylene (HATN) and dibenzo-[a,c]- phenazine as aromatic cores, changing different side chains to control the mesomorphic behavior and their supermolecular assembly.