Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are common contaminants of sediment, soils and biological tissues. These compounds pose a significant risk to biological and ecosystem health and functioning due to these compounds being mutagenic, carcinogenic and are known to disrupt the endocrine system. The bioaccumulation and biomagnification potential that these compounds possess mean that they are capable of affecting the entire food chain and are not limited to the organisms that are directly in contact with the compounds Even though there has been an increase in the attention on identifying the presence and impacts that these compounds may have in South Africa, the level of attention is lower than what it is in other countries around the world. Although South Africa has guidelines in place for other pollutants, such as metals, there are no such guidelines in place to monitor PAHs and PCBs.. Industries are known to release both PAHs and PCBs, mainly from incomplete burning processes and the release of oils and fuels in the case of PAHs, and from heat transfer fluids in the case of PCBs. Durban Bay and surrounding areas of eThekwini, KwaZulu-Natal are highly industrialised with many aquatic systems, in which these contaminants are likely to deposit. The aim of this research was to determine the concentrations of these compounds by means of chemical analysis and additionally biological analysis, using the H4IIE-luc bioassay and compare these levels to international guideline levels. It was found that the concentrations of the 23 analysed PAHs were 6.5–3 235.6 ng.g-1 and the concentration of the PCBs analysed were 0–113.83 ng.g-1. Many sites were found to be in exceedance of the guideline limits, particularly in the harbour. Toxic equivalency factors (TEF) were used to gauge the toxic equivalency (TEQ) of the PAHs and PCBs that were found. The TEQs were generally low, and were below any guideline levels. The assay revealed the extract containing the PCBs had a bioassay equivalence (BEQ) of 0–93.54 pgTCDDeq. g-1 and the extract containing the PAHs of 0–776.08 pgTCDD-eq.g-1. With a proportion of the sites exceeding guideline limits. The BEQ results were two to three orders of magnitude greater than the TEQs calculated from the concentrations determined by the instrumental analysis, however, followed a similar trend. Additionally chemical analysis was not performed on a full suite of compounds that are able to elicit a response from the cells, which could be a reason why the BEQ and TEQ did not follow a similar trend among some of the samples. It would have been more beneficial to have performed chemical analysis on the 16 priority PAHs (as determined by the United States Environmental Protection Agency), the dioxin-like PCBs and polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDFs) which are all capable of eliciting a response from the cells and have TEF values. The areas that were most affected by contamination of these compounds was the harbour and surrounding canals, and there was point source contamination along the Umhlatuzana, Umbilo, and Amanzimnyana Rivers. All dl-PCBs should be chemically analysed at all the sample areas, as these cause adverse effects to biota. In addition to this, biota should be sampled to determine concentrations of the compounds to determine bioavailability and the degree of bioaccumulation in the food chain. Utilising biomarkers it would be possible to determine stresses of fish. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2014

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are common contaminants of sediment, soils and biological tissues. These compounds pose a significant risk to biological and ecosystem health and functioning due to these compounds being mutagenic, carcinogenic and are known to disrupt the endocrine system. The bioaccumulation and biomagnification potential that these compounds possess mean that they are capable of affecting the entire food chain and are not limited to the organisms that are directly in contact with the compounds Even though there has been an increase in the attention on identifying the presence and impacts that these compounds may have in South Africa, the level of attention is lower than what it is in other countries around the world. Although South Africa has guidelines in place for other pollutants, such as metals, there are no such guidelines in place to monitor PAHs and PCBs.. Industries are known to release both PAHs and PCBs, mainly from incomplete burning processes and the release of oils and fuels in the case of PAHs, and from heat transfer fluids in the case of PCBs. Durban Bay and surrounding areas of eThekwini, KwaZulu-Natal are highly industrialised with many aquatic systems, in which these contaminants are likely to deposit. The aim of this research was to determine the concentrations of these compounds by means of chemical analysis and additionally biological analysis, using the H4IIE-luc bioassay and compare these levels to international guideline levels. It was found that the concentrations of the 23 analysed PAHs were 6.5–3 235.6 ng.g-1 and the concentration of the PCBs analysed were 0–113.83 ng.g-1. Many sites were found to be in exceedance of the guideline limits, particularly in the harbour. Toxic equivalency factors (TEF) were used to gauge the toxic equivalency (TEQ) of the PAHs and PCBs that were found. The TEQs were generally low, and were below any guideline levels. The assay revealed the extract containing the PCBs had a bioassay equivalence (BEQ) of 0–93.54 pgTCDDeq. g-1 and the extract containing the PAHs of 0–776.08 pgTCDD-eq.g-1. With a proportion of the sites exceeding guideline limits. The BEQ results were two to three orders of magnitude greater than the TEQs calculated from the concentrations determined by the instrumental analysis, however, followed a similar trend. Additionally chemical analysis was not performed on a full suite of compounds that are able to elicit a response from the cells, which could be a reason why the BEQ and TEQ did not follow a similar trend among some of the samples. It would have been more beneficial to have performed chemical analysis on the 16 priority PAHs (as determined by the United States Environmental Protection Agency), the dioxin-like PCBs and polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDFs) which are all capable of eliciting a response from the cells and have TEF values. The areas that were most affected by contamination of these compounds was the harbour and surrounding canals, and there was point source contamination along the Umhlatuzana, Umbilo, and Amanzimnyana Rivers. All dl-PCBs should be chemically analysed at all the sample areas, as these cause adverse effects to biota. In addition to this, biota should be sampled to determine concentrations of the compounds to determine bioavailability and the degree of bioaccumulation in the food chain. Utilising biomarkers it would be possible to determine stresses of fish. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2014

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) are omnipresent and persistent environmental pollutants. In particular, 29 congeners are of special concern, and these are usually referred to as dioxin-like compounds (DLCs). In the European Union, the risks associated with DLCs in food products are estimated by a weighted sum of the DLCs’ concentrations. These weights, also called toxic equivalency factors (TEFs), compare the DLCs’ potencies to the most toxic congener, 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2378- TCDD). The toxicological effects of PCDD/Fs and PCBs are diverse, ranging from chloracne and immunological effects in humans to severe weight loss, thymic atrophy, hepatotoxicity, immunotoxicity, endocrine disruption, and carcinogenesis in rodents. Here, the molecular structures of DLCs were used as the basis to study the congeneric differences in in vitro data from both human and rodent cell responses related to the aryl hydrocarbon receptor (AhR). Based on molecular orbital densities and partial charges, we developed new ways to describe DLCs, which proved to be useful in quantitative structure-activity relationship modeling. This thesis also provides a new approach, the calculation of the consensus toxicity factor (CTF), to condense information from a battery of screening tests. The current TEFs used to estimate the risk of DLCs in food are primarily based on in vivo information from rat and mouse experiments. Our CTFs, based on human cell responses, show clear differences compared to the current TEFs. For instance, the CTF of 23478-PeCDF is as high as the CTF for 2378-TCDD, and the CTF of PCB 126 is 30 times lower than the corresponding TEF. Both of these DLCs are common congeners in fish in the Baltic Sea. Due to the severe effects of DLCs and their impact on environmental and human health, it is crucial to determine if other compounds have similar effects. To find such compounds, we developed a virtual screening protocol and applied it to a set of 6,445 industrial chemicals. This protocol included a presumed 3D representation of AhR and the structural and chemical properties of known AhR ligands. This screening resulted in a priority list of 28 chemicals that we identified as potential AhR ligands.