Contaminated soils and sediments have been identified as significant secondary sources of organic contaminants.  Leaching tests may be useful tools to estimate the mobility of contaminants via the water phase and thereby the risk for groundwater and surface water contamination. The influence of soil composition (peat and clay content) on the leachability was investigated in batch leaching experiments for chemically diverse hydrophobic organic compounds (HOCs: PCP, PAHs, HCB, HCHs, PCBs, and TCDD/Fs). The above mentioned compounds were analyzed by both GC-LRMS (gas chromatography coupled with low resolution mass spectrometry (GC-HRMS) and GC-HRMS (gas chromatography coupled with high resolution mass spectrometry). Also the the leachability of eleven selected PCBs from naturally aged soil (Västervik, Sweden) was investigated in relation to the composition and concentration of dissolved organic matter at different pH (2 to 9), using a pH static test with initial acid/base addition. The the composition and of dissolved organic matter (DOM) at different pH values was explored by FTIR spectroscopy. The results were evaluated by orthogonal projections to latent structures (OPLS). Generally, for all model compounds studies, the Kd-values showed a variability of 2-3 orders of magnitude depending on the matrix composition. The Kd-values of moderately hydrophobic compounds, (e.g. HCHs, PCP and Phe), were correlated mainly with the organic matter content of soil. For more hydrophobic compounds (e.g.BaA, HCB and PCB 47), the leachability decreased as the proportions of  OM and clay contents increased. The Kd-values of 1,3,6,8-TCDD and 1,3,6,8-TCDF were  positively correlated with peat content but negatively correlated with clay content, while for PCB 153 and PCB 155 the correlations were reversed. The log Kd-values of all target PCBs decreased with increased pH values and the log Kd-values were highly correlated with the concentration of total organic carbon (TOC) in the leachates. The FTIR analysis of DOM showed that the least chlorinated and hydrophobic PCB congeners (i.e. PCB 28) might be associated with the hydrophilic fraction (i.e. carboxylic groups) of DOM. Our study demonstrated how complex interaction between the organic matter, clay components, pH and DOC influences the leachability of HOCs in a compound-specific manner.

South Africa ratified the Stockholm Convention (SC), which became legally binding on 17 May 2004. This Convention targets 12 particularly toxic persistent organic pollutants (POPs) for virtual elimination. The Convention also requires parties to reduce the release of organochlorine pesticides and the intentionally- and unintentionally-produced POPs such as dioxins, furans and polychlorinated biphenyls (PCBs) (referred to as dioxin-like chemicals). Dioxins are a heterogeneous mixture of chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) congeners. These substances were never intentionally produced but are produced as by-products of industrial processes (such as metallurgical processes and bleaching of paper pulp). They can also be formed during natural processes such as volcanic eruptions and forest fires. The largest contributor to releases of PCDD/Fs in the environment is incomplete combustion from waste incinerators leading to the unintentional production of these compounds. Polychlorinated biphenyls (PCBs) are used in transformers and capacitors, but can also be formed unintentionally during industrial and thermal processes. Dioxin-like chemicals (PCDD/Fs and/or PCBs) are classified as persistent because of the following characteristics: lipophilicity and hydrophobicity; resistance to photolytic, chemical and biological degradation and they are able to travel long distances. As South Africa is a semiarid region, POPs will be less prone to travel here because these substances favour colder regions with high soil organic matter. Fish, predatory birds, mammals (including humans) absorb high concentrations of POPs through the process of bio-concentration, leading to bio-accumulation of these substances in the fatty tissue. PCDD/Fs occur as unwanted trace contaminants in air, water, land, in residues and products (such as consumer goods e.g. paper and textiles). The distribution of these chemicals into various matrices is problematic since they cause damage to the environment and human health. These chemicals pose a threat to human health when found in high concentrations that may lead to acute hepatoxicity and dermal toxicity (chloracne). Long-term exposure to low concentrations of these substances might lead to chronic effects such as reproductive problems and carcinogenicity. Since ferrous and non-ferrous metal production is a source of dioxin-like chemicals, a platinum mine in the Limpopo Province, South Africa, was selected for this investigation. The aim of the study was to determine if there are dioxin-like chemicals associated with platinum mining and processing, and if the H4IIE reporter gene bio-assay could be used to semi-quantify and assess the potencies of the complex environmental and process samples by determining their Toxic Equivalency Quotients (TEQ). The implications of the sources to the formation of dioxin-like chemicals regarding the SC were investigated and recommendations were made to improve this study. Samples were collected from tailings dams, woodchips, a dumpsite and slag from the smelter at Union Section. Samples were extracted with the Soxhlet apparatus using hexane as solvent. The percentage total organic carbon (%TOC) was determined for each sample to normalise the data. The method used was the Walkley-Black method. In determining the TEQ of each sample, the H4IIE luc cell line was used. The cells of the H4IIE luc line are genetically modified rat hepatoma cells stably transfected with a luciferase firefly gene. The luciferase gene is activated by the presence of dioxin-like compounds and the concentration of the enzyme is measured as relative light units (RLUs). The amount of RLUs is directly proportional to the dioxin load in the extract. This method is rapid, cost and time-effective in determining the TEQ when compared to chemical analysis. The TEQ2o-valuesin the various samples, as determined with the H4IIE luc cell line, ranged from 0.007 ngTEQ/kg to 54.06 ngTEQ/kg. Thermal processes at the smelter, sorption of hydrophobic organic compounds (HOCs) to soil and tailings, and external sources such as anthropogenic activities contributed to high TEQ2o-values. Climatic conditions, wind, precipitation, and solubility of HOCs into surfactants lead to low TEQ20. The smelter at Union Section had a very high TEQ20of 44.62 ngTEQ/kg compared to Impala Platinum mine (5.15 ngTEQ/kg). This implies that workers at Union Section are possibly exposed to low and high concentrations of dioxin-like chemicals. Long-term exposure to these compounds could lead to bio-accumulation in the fatty tissue of the mine workers, leading to chronic effects such as reproductive problems and cancer. The air emission of the furnace at the smelter was 0.03 gTEQ/annum and the release of the PCDD/Fs into the slag was 0.60 gTEQ/annum. By effectively managing the smelter it is possible to reduce the TEQ. The TEQ of each sample increased due to normalising the data. The normalised TEQ20 ranged from 0.94 ng TEQ/kg to 42497.48 ngTEQ/kg. Dioxin-like chemicals are present on a platinum mine, but at varying quantities and the effects of these compounds might be detrimental to the environment and the workers at the platinum mine. Further analyses of the health impacts associated with the platinum mine are needed. The H4IIE reporter gene bio-assay could be used to effectively determine the TEQ of each sample. Although this investigation has identified the formation and presence of dioxin-like chemicals at certain stages of mining and processing, not all of the processes were investigated. Some of these processes have the potential to add, and even destroy, these chemicals, affecting potential human exposure and amounts released to the environment. This, however, requires further investigation. The financial assistance of the National Research Foundation (NRF) towards this research is hereby acknowledged. Opinions expressed and conclusions arrived at, are those of the author and are not necessarily to be attributed to the NRF. / Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2006.

South Africa ratified the Stockholm Convention (SC), which became legally binding on 17 May 2004. This Convention targets 12 particularly toxic persistent organic pollutants (POPs) for virtual elimination. The Convention also requires parties to reduce the release of organochlorine pesticides and the intentionally- and unintentionally-produced POPs such as dioxins, furans and polychlorinated biphenyls (PCBs) (referred to as dioxin-like chemicals). Dioxins are a heterogeneous mixture of chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) congeners. These substances were never intentionally produced but are produced as by-products of industrial processes (such as metallurgical processes and bleaching of paper pulp). They can also be formed during natural processes such as volcanic eruptions and forest fires. The largest contributor to releases of PCDD/Fs in the environment is incomplete combustion from waste incinerators leading to the unintentional production of these compounds. Polychlorinated biphenyls (PCBs) are used in transformers and capacitors, but can also be formed unintentionally during industrial and thermal processes. Dioxin-like chemicals (PCDD/Fs and/or PCBs) are classified as persistent because of the following characteristics: lipophilicity and hydrophobicity; resistance to photolytic, chemical and biological degradation and they are able to travel long distances. As South Africa is a semiarid region, POPs will be less prone to travel here because these substances favour colder regions with high soil organic matter. Fish, predatory birds, mammals (including humans) absorb high concentrations of POPs through the process of bio-concentration, leading to bio-accumulation of these substances in the fatty tissue. PCDD/Fs occur as unwanted trace contaminants in air, water, land, in residues and products (such as consumer goods e.g. paper and textiles). The distribution of these chemicals into various matrices is problematic since they cause damage to the environment and human health. These chemicals pose a threat to human health when found in high concentrations that may lead to acute hepatoxicity and dermal toxicity (chloracne). Long-term exposure to low concentrations of these substances might lead to chronic effects such as reproductive problems and carcinogenicity. Since ferrous and non-ferrous metal production is a source of dioxin-like chemicals, a platinum mine in the Limpopo Province, South Africa, was selected for this investigation. The aim of the study was to determine if there are dioxin-like chemicals associated with platinum mining and processing, and if the H4IIE reporter gene bio-assay could be used to semi-quantify and assess the potencies of the complex environmental and process samples by determining their Toxic Equivalency Quotients (TEQ). The implications of the sources to the formation of dioxin-like chemicals regarding the SC were investigated and recommendations were made to improve this study. Samples were collected from tailings dams, woodchips, a dumpsite and slag from the smelter at Union Section. Samples were extracted with the Soxhlet apparatus using hexane as solvent. The percentage total organic carbon (%TOC) was determined for each sample to normalise the data. The method used was the Walkley-Black method. In determining the TEQ of each sample, the H4IIE luc cell line was used. The cells of the H4IIE luc line are genetically modified rat hepatoma cells stably transfected with a luciferase firefly gene. The luciferase gene is activated by the presence of dioxin-like compounds and the concentration of the enzyme is measured as relative light units (RLUs). The amount of RLUs is directly proportional to the dioxin load in the extract. This method is rapid, cost and time-effective in determining the TEQ when compared to chemical analysis. The TEQ2o-valuesin the various samples, as determined with the H4IIE luc cell line, ranged from 0.007 ngTEQ/kg to 54.06 ngTEQ/kg. Thermal processes at the smelter, sorption of hydrophobic organic compounds (HOCs) to soil and tailings, and external sources such as anthropogenic activities contributed to high TEQ2o-values. Climatic conditions, wind, precipitation, and solubility of HOCs into surfactants lead to low TEQ20. The smelter at Union Section had a very high TEQ20of 44.62 ngTEQ/kg compared to Impala Platinum mine (5.15 ngTEQ/kg). This implies that workers at Union Section are possibly exposed to low and high concentrations of dioxin-like chemicals. Long-term exposure to these compounds could lead to bio-accumulation in the fatty tissue of the mine workers, leading to chronic effects such as reproductive problems and cancer. The air emission of the furnace at the smelter was 0.03 gTEQ/annum and the release of the PCDD/Fs into the slag was 0.60 gTEQ/annum. By effectively managing the smelter it is possible to reduce the TEQ. The TEQ of each sample increased due to normalising the data. The normalised TEQ20 ranged from 0.94 ng TEQ/kg to 42497.48 ngTEQ/kg. Dioxin-like chemicals are present on a platinum mine, but at varying quantities and the effects of these compounds might be detrimental to the environment and the workers at the platinum mine. Further analyses of the health impacts associated with the platinum mine are needed. The H4IIE reporter gene bio-assay could be used to effectively determine the TEQ of each sample. Although this investigation has identified the formation and presence of dioxin-like chemicals at certain stages of mining and processing, not all of the processes were investigated. Some of these processes have the potential to add, and even destroy, these chemicals, affecting potential human exposure and amounts released to the environment. This, however, requires further investigation. The financial assistance of the National Research Foundation (NRF) towards this research is hereby acknowledged. Opinions expressed and conclusions arrived at, are those of the author and are not necessarily to be attributed to the NRF. / Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2006.

Passive sampling, as opposed to the conventional spot or bottle water sampling technique, has shown to be reliable and efficient in monitoring the toxicologically relevant, freely dissolved (e.g. bioavaialable) concentrations of a wide range of organic contaminants in water. At the same time, partitioning controlled delivery (passive dosing; PD) techniques promise to overcome many of the challenges associated with toxicity testing of hydrophobic substances that may bias the interpretation of toxicity data. The present study investigated the feasibility of coupling silicone rubber passive sampling devices (SR-PSDs) with bioassay techniques for both chemical and ecotoxicological assessment of complex mixtures of organic contaminants in the aquatic environment. SR-PSDs were deployed in water at various locations within the Ythan catchment (north east, Scotland, UK), Forth estuary and the Firth of Forth (east coast of central Scotland, UK) for 7 to 9 weeks. Following retrieval, extracts from the SR-PSDs were analysed for dissolved concentrations of a variety of organic contaminants including PAHs and PCBs using GC-MS and GC-ECD respectively and were screened for a wide range of pesticides using GC-MS/MS and LC-MS/MS. The extracts were further evaluated for acute cytotoxicity (i.e. neutral red uptake assay) and EROD induction potential using rainbow trout liver cell line (Oncorhynchus mykiss; RTL-W1) and for phytotoxicity and developmental toxicity potential using algal growth inhibition test (with a marine phytoplankton, Diacronema lutheri) and fish embryo toxicity test (with embryos from zebrafish Danio rerio) respectively. Overall, the individual and total dissolved concentrations of PAHs (ΣPAH40; parent and branched) and PCBs (ΣPCB32; ortho and mono-ortho) measured in water from the Ythan, Forth estuary and Firth of Forth were relatively low compared with other studies using PSDs. A number and level of pesticides, including insecticides, herbicides and fungicides of varying hydrophobicity (log KOWs ~2.25 to ~5.31) were detected in the silicone rubber (SR) extracts from the Ythan catchment, the Forth estuary and the Firth of Forth, suggesting input mainly from agricultural run-off and possibly from direct discharges. No statistically significant (p<0.05) acute cytotoxicity was observed following 48 h exposure of RTL-W1 cells to SR extracts from the Ythan catchment. But, on a sublethal level, for every site, statistically significant EROD activity was observed to some degree following 72 h exposure. In addition, developmental and algal toxicities on embryos of D. rerio and D. lutheri respectively, were measured in all the deployed samples compared with the procedural controls (undeployed samples). Interestingly, extracts of SR-PSDs from the Forth estuary and the Firth of Forth exhibited growth inhibitions on D. lutheri that were similar to those of extracts from the Ythan, even though, fewer numbers of pesticides were detected in the Forth estuary and Firth of Forth than the Ythan. This suggests that pesticides were not solely responsible for the observed effects in the Ythan catchment. To further improve data from toxicity testing of hydrophobic substances, the study identified the use of SR O-rings as a suitable passive dosing format in in vitro toxicity tests and was partially validated through their use in dosing RTL-W1 cells with two individual PAHs and subsequently determining cytotoxicity and EROD-activity.