Estuaries are among the most productive and diverse of aquatic habitats supporting a rich variety of plants and animals. They are nursery areas for many species of fish harvested by recreational and subsistence anglers. The Swartkops River Estuary (SRE) is situated approximately 10 km north-east of Port Elizabeth and the only major well-preserved estuary within a city, thus unique to South Africa. The SRE is surrounded by highly urbanized and industrialized regions in the Eastern Cape. The aim of this study was to determine and interpret the presence, levels, and distribution of selected priority pollutants in the food web of the SRE. Different components within the SRE were analysed for the presence of environmental contaminants. Seven sites were selected, some coinciding with previous studies in the SRE. Three of these sites are major discharge points that discharge directly into the estuary. Sediment, mud prawn, sand gobies, bird eggs, and various fish species were analysed. Samples were collected in the middle and lower reaches of the estuary, the areas known to receive major pollution loads from neighbouring sources. Heavy metals found in the sediments were compared to previous studies. Bottom sediments and organisms surrounding major discharge points showed higher concentrations of pollutants and compared to previous studies, these concentrations seem to be increasing. Due to biomagnification, higher concentrations were generally found in the top predators although certain elements did not show this trend. Some heavy metal concentrations found in the fish exceeded of the food guidelines and may in turn pose a threat for subsistence users of the SRE. There are indications of multiple different pollution sources. Bird eggs had detectable quantities of polychlorinated biphenyls, but its implications need more investigation. / MSc (Zoology), North-West University, Potchefstroom Campus, 2014

Estuaries are among the most productive and diverse of aquatic habitats supporting a rich variety of plants and animals. They are nursery areas for many species of fish harvested by recreational and subsistence anglers. The Swartkops River Estuary (SRE) is situated approximately 10 km north-east of Port Elizabeth and the only major well-preserved estuary within a city, thus unique to South Africa. The SRE is surrounded by highly urbanized and industrialized regions in the Eastern Cape. The aim of this study was to determine and interpret the presence, levels, and distribution of selected priority pollutants in the food web of the SRE. Different components within the SRE were analysed for the presence of environmental contaminants. Seven sites were selected, some coinciding with previous studies in the SRE. Three of these sites are major discharge points that discharge directly into the estuary. Sediment, mud prawn, sand gobies, bird eggs, and various fish species were analysed. Samples were collected in the middle and lower reaches of the estuary, the areas known to receive major pollution loads from neighbouring sources. Heavy metals found in the sediments were compared to previous studies. Bottom sediments and organisms surrounding major discharge points showed higher concentrations of pollutants and compared to previous studies, these concentrations seem to be increasing. Due to biomagnification, higher concentrations were generally found in the top predators although certain elements did not show this trend. Some heavy metal concentrations found in the fish exceeded of the food guidelines and may in turn pose a threat for subsistence users of the SRE. There are indications of multiple different pollution sources. Bird eggs had detectable quantities of polychlorinated biphenyls, but its implications need more investigation. / MSc (Zoology), North-West University, Potchefstroom Campus, 2014

Polybrominated flame retardants (BFRs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were analysed in eggs of various wild bird species from industrialised areas in South Africa. Eggs were collected during the 2008 – 2009 breeding season, homogenised and sent to the Norwegian School of Veterinary Science (NVH) for gas chromatography-mass spectrometry (GC-MS) analysis. The concentration, contamination profile, and risk assessment were conducted for each pollutant class, while effects of species-specific variation, feeding guild, and feeding habitat were investigated. Levels of BFRs ranged between 2.6 – 44 ng g-1 wet mass (wm). The predominant congeners were BDE-153, -154, - 183 and -47. Results indicated species, in close contact to humans, had higher levels of BFRs, even at lower trophic levels. Therefore, diet was not the primary route of exposure. High concentrations and the occurrence of nona-PBDE congeners and HBCD indicated exposure to current use BFRs. There were measurable levels of OCPs and PCBs in all eggs analysed. Median OCP concentration ranged from 4.2 – 623 ng g-1 wm. DDE was the predominant compound in all species with the exception of the Crowned Lapwing (Vanellus coronatus) where chlordanes were predominant. This may indicate a species-specific attribute in the metabolic efficiency or diet of the genus, since these findings have been reported elsewhere in literature. Congener profiles indicated historic sources of lindane and DDT, while low levels of p,p’-DDT in al species indicate long-range or atmospheric transport. Even though levels of p,p’-DDE were approaching toxicological thresholds, no eggshell thinning was evident. Concentrations of OCPs and PCBs showed an increase with increasing tophic level. PCB concentrations ranged between 0.9 – 296.4 ng g-1 wm. When studying the metabolic potential of PCBs, metabolic groups showed good agreement with the biodegradability of the individual congeners. Phenobarbital-type (PB-type) inducer PCBs were prevalent, indicating the predominance of less toxic PCB congeners. However, non-ortho PCBs were not analysed. These congeners aslo could impact on the toxic potential of PCBs in wild bird eggs. Principle component analysis (PCA) indicated that variances within datasets could be attributed to congener profiles within species as they were affected by exposure, diet, position in the food web, and association with human activities. Although the individual groups of organohalogens were below no observed effect levels (NOELs), negative effects could occur through interactions of various compounds with each other, as well as the unique exposure profiles of South African bird populations. To assess the dietary exposure of low-income human populations living close to large industries, the occurrence of organohalogens was investigated in backyard chicken eggs. Levels of dioxins in these eggs were above the European Union (EU) recommended limits, whereas BFRs and OCPs levels were below levels of concern. Nevertheless, areas where DDT is actively applied to dwellings for malaria control should be urgently investigated. The presence of measureable levels of all the compounds considered, indicate an environment seriously impacted by anthropogenic activity that in the long term could negatively affect both the environment and human health, if it has not already done so. / Thesis (Ph.D. (Environmental Science))--North-West University, Potchefstroom Campus, 2011.

Polybrominated flame retardants (BFRs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were analysed in eggs of various wild bird species from industrialised areas in South Africa. Eggs were collected during the 2008 – 2009 breeding season, homogenised and sent to the Norwegian School of Veterinary Science (NVH) for gas chromatography-mass spectrometry (GC-MS) analysis. The concentration, contamination profile, and risk assessment were conducted for each pollutant class, while effects of species-specific variation, feeding guild, and feeding habitat were investigated. Levels of BFRs ranged between 2.6 – 44 ng g-1 wet mass (wm). The predominant congeners were BDE-153, -154, - 183 and -47. Results indicated species, in close contact to humans, had higher levels of BFRs, even at lower trophic levels. Therefore, diet was not the primary route of exposure. High concentrations and the occurrence of nona-PBDE congeners and HBCD indicated exposure to current use BFRs. There were measurable levels of OCPs and PCBs in all eggs analysed. Median OCP concentration ranged from 4.2 – 623 ng g-1 wm. DDE was the predominant compound in all species with the exception of the Crowned Lapwing (Vanellus coronatus) where chlordanes were predominant. This may indicate a species-specific attribute in the metabolic efficiency or diet of the genus, since these findings have been reported elsewhere in literature. Congener profiles indicated historic sources of lindane and DDT, while low levels of p,p’-DDT in al species indicate long-range or atmospheric transport. Even though levels of p,p’-DDE were approaching toxicological thresholds, no eggshell thinning was evident. Concentrations of OCPs and PCBs showed an increase with increasing tophic level. PCB concentrations ranged between 0.9 – 296.4 ng g-1 wm. When studying the metabolic potential of PCBs, metabolic groups showed good agreement with the biodegradability of the individual congeners. Phenobarbital-type (PB-type) inducer PCBs were prevalent, indicating the predominance of less toxic PCB congeners. However, non-ortho PCBs were not analysed. These congeners aslo could impact on the toxic potential of PCBs in wild bird eggs. Principle component analysis (PCA) indicated that variances within datasets could be attributed to congener profiles within species as they were affected by exposure, diet, position in the food web, and association with human activities. Although the individual groups of organohalogens were below no observed effect levels (NOELs), negative effects could occur through interactions of various compounds with each other, as well as the unique exposure profiles of South African bird populations. To assess the dietary exposure of low-income human populations living close to large industries, the occurrence of organohalogens was investigated in backyard chicken eggs. Levels of dioxins in these eggs were above the European Union (EU) recommended limits, whereas BFRs and OCPs levels were below levels of concern. Nevertheless, areas where DDT is actively applied to dwellings for malaria control should be urgently investigated. The presence of measureable levels of all the compounds considered, indicate an environment seriously impacted by anthropogenic activity that in the long term could negatively affect both the environment and human health, if it has not already done so. / Thesis (Ph.D. (Environmental Science))--North-West University, Potchefstroom Campus, 2011.

Per-and polyfluoroalkyl substances (PFAS) are anthropogenic compounds that have been spread all over the world. The use of fluorotelomer compounds, short-chained homologues, and other PFASs with perfluorinated moieties has emerged recent years. One of these emerging compound classes is polyfluoroalkyl phosphate esters (PAPs), which have the ability to degrade into persistent PFCAs. The aim of this thesis was to assess the contribution of PAPs and other precursors to the exposure of PFCAs to humans and the environment. The main objective was to analyze a wide range of PFAS in human serum, wild bird eggs, indoor dust, waste water, and sludge. There was a significant contribution from selected precursors to the total amount of PFASs in the abiotic compartments indoor dust, waste water, and sludge. Levels of PAPs found in house dust exceeded those of PFCAs and perfluorosulfonic acids (PFSAs), revealing PAPs as a world-wide important exposure source. A net increase was during waste water treatment was observed for several PFASs in Swedish waste water treatment plants. Together with presence of precursor compounds and intermediates in the influent water and the sludge, this suggest that degradation of PFCA precursors contributed to the increase of PFCAs. Detection of precursors in human serum, together with slow declining trends of PFCAs, revealed an ongoing exposure of PFCAs to the general population of Australia. The diPAPs and the FTSAs were also detected in raptor bird eggs from Sweden from both the terrestrial and the freshwater environment. The precursors concentrations and patterns observed reveal that current regulatory measures are insufficient for the purpose of protecting humans and the environment from PFASs exposure.

Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure. The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design. The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs). A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner. The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Submitted. Paper 6: Manuscript.</p><p> </p>

The thesis deals with several aspects of monitoring of persistent organic contaminants (POPs) in biological matrices, for example choice of sample, sampling design, and statistical treatment of data both for temporal and spatial trends and for compliance towards a set target value. The efficiency has been evaluated through statistical power analyses. Contaminant data from more than 4 decades from the Swedish National Monitoring Programs for monitoring of contaminants in biota (marine, freshwater and human health), has been quantitatively evaluated both temporally and spatially and for compliance. The aim was also to evaluate the suitability of different matrices, i.e. herring (Clupea harengus), guillemot (Uria aalge) egg, cod (Gadus morhua), perch (Perca fluviatilis), eelpout (Zoarces viviparous), blue mussel (Mytilus edulis), pike (Esox lucius), Arctic char (Salvelinus alpinus) and human milk, for monitoring of POPs with the overall aim to improve the assessment within monitoring programs. The results show that variation can be reduced by using pooled samples including more specimens but fewer chemical analyses, which in turn generate a higher statistical power to a lower cost, at least in cases where the cost of collection and sampling is considerably lower than the cost of chemical analysis. However, there are also a number of advantages using individual samples, such as information of sample variance and maximum value, which allows the choice of an appropriate central measure and direct adjustment of confounding factors. Generally, the levels of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) have decreased both in marine and freshwater biota but concentrations are still higher in the Baltic compared to e.g. the North Sea. The levels of dioxinlike-PCBs and polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) have decreased in human milk over time, but not to the same extent in fish and guillemot egg from the Baltic and the freshwater environment. This may be explained by the dietary advice developed by the Swedish Food Administration with the goal that girls, reproductive aged, and pregnant women should eat less food containing high levels of PCDD/Fs. Thus the levels in milk could continue to decrease at the same rate although the temporal trend in the environment has slowed down or leveled out. The most essential regarding the choice of species and matrices for contaminant monitoring, is that the species and organ fit the purpose of the monitoring.

Per- and polyfluoroalkyl substances (PFASs) are a group of toxic and persistent organic compounds. Their properties make them extremely resistant and they have been shown to have bioaccumulation and toxic properties in the environment and also to biomagnify in both aquatic and terrestrial food webs. This study has analysed different PFASs in African Darter (Anhinga rufa) eggs from five sites along Vaal River; Orange River, South Africa. Sixteen of 23 analysed PFASs were detected and quantified, and the homologue profiles were studied from all five sites. Total perfluorooctane sulfonic acid (PFOS) (all structural isomers) was the predominated compound of all PFASs, accounting for 88-98% for all sites, with a median concentration range of 58 ng/g ww to 2473 ng/g ww. The second highest concentration was found for perfluorodecanoic acid (PFDA) (1.9-42 ng/g ww), followed by perfluorononanoic acid (PFNA) (1.1-14 ng/g ww) and perfluorohexane sulfonate (PFHxS) (0.68-6.0 ng/g ww). The results showed significantly that the three up-stream sites (Welverdiend, Schoemansdrift and Orkney East) had similar patterns and that eggs from Schoemansdrift had the highest levels of PFASs. This may indicate the same source of origin for these three sites and that Schoemansdrift are closest to the contamination source. The three sites (Welverdiend, Schoemansdrift and Orkney East) with similar pattern is closest to Gauteng, which can be where the emission source is located, because it is an industrial area. Perfluoroalkyl carboxylic acids (PFCAs) and PFOS might originate from different sources and the source for PFCAs could be degradation of fluorotelomer-based precursors. Structural isomer profiles of PFOS showed similar results as the PFAS homologue patterns, which give further indication of the source of origin. The contribution of linear PFOS (L-PFOS) to the total amount of PFOS was between the range of 94 and 97%. Bloemhof had the highest concentration of branched isomers among all sites. The L-PFOS concentrations in Bloemhof were also significantly differ from Schoemansdrift. This indicate two different sources between Bloemhof and the three up-steam sites, or an effect of environmental fractionation.