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>

Persistent organic pollutants (POPs) is a group of chemicals that are toxic, undergo long-range transport and accumulate in biota. Due to their persistency the distribution and recirculation in the environment often continues for a long period of time. Thereby they appear virtually everywhere within the biosphere, and poses a toxic stress to living organisms. In this thesis, attempts are made to contribute to the understanding of factors that influence the distribution of POPs with focus on processes in the marine environment. The bioavailability and the spatial distribution are central topics for the environmental risk management of POPs. In order to study these topics, various field studies were undertaken. To determine the bioavailable fraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), and polychlorinated biphenyls (PCBs) the aqueous dissolved phase were sampled and analysed. In the same samples, we also measured how much of these POPs were associated with suspended particles. Different models, which predicted the phase distribution of these POPs, were then evaluated. It was found that important water characteristics, which influenced the solid-water phase distribution of POPs, were particulate organic matter (POM), particulate soot (PSC), and dissolved organic matter (DOM). The bioavailable dissolved POP-phase in the water was lower when these sorbing phases were present. Furthermore, sediments were sampled and the spatial distribution of the POPs was examined. The results showed that the concentration of PCDD/Fs, and PCNs were better described using PSC- than using POM-content of the sediment. In parallel with these field studies, we synthesized knowledge of the processes affecting the distribution of POPs in a multimedia mass balance model. This model predicted concentrations of PCDD/Fs throughout our study area, the Grenlandsfjords in Norway, within factors of ten. This makes the model capable to validate the effect of suitable remedial actions in order to decrease the exposure of these POPs to biota in the Grenlandsfjords which was the aim of the project. Also, to evaluate the influence of eutrophication on the marine occurrence PCB data from the US Musselwatch and Benthic Surveillance Programs are examined in this thesis. The dry weight based concentrations of PCB in bivalves were found to correlate positively to the organic matter content of nearby sediments, and organic matter based concentrations of PCB in sediments were negatively correlated to the organic matter content of the sediment.

Concern on a global scale gave rise to the founding of the Stockholm Convention on persistent organic pollutants (POPs) with a view to restrict the use and production of these toxic chemicals. As a signatory, South Africa is legally bound to abide to the Convention’s objectives, including participating in relevant research and monitoring. However, developing countries such as South Africa have limited information concerning POPs, partially because these countries do not have sufficient analytical capabilities, and thus method development and refinement are necessary. One group of POPs consisting of polychlorinated dibenzo-pdioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs), collectively referred to as dioxins, are of particular concern due to their high toxicity and persistence. Additionally, the analysis of dioxins is recognised as one of the most analytically challenging of its kind. This study investigated the effect of different preparatory protocols on the semi-quantification of dioxins using the H4IIE-luc-reporter gene assay. The protocols evaluated were either Soxhlet or pressurised liquid extraction (PLE) combined with a manual acid digestion, gel permeation chromatography (GPC) and Florisil fractionation clean-up procedure as well as the automated Total Rapid Prep™(TRP) system which makes use of a PLE combined with a multi-layer silica, alumina and carbon column clean-up procedure. To evaluate the protocols, an eight point matrix matched calibration curve, two soil samples and a certified reference material (CRM) were used. The extracts were semi-quantified by the H4IIE-luc bio-assay. During the course of the assay, the appropriateness of different standards was investigated, and a mixed standard containing all 17 toxic PCDD/Fs was chosen for quantification. During the data review process, higher bioassay equivalent (BEQ) values were obtained from PLE compared to Soxhlet extraction, while no statistically significant difference (Kruskal-Wallis ANOVA: p > 0.05) was found between the assay quantifications for the different preparatory techniques. However, the results of the H4IIE bio-assay were larger than the expected values. The identity of the chemicals that were in all likelihood responsible for the higher response was investigated through instrumental analysis using comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GCxGC-TOFMS). Instrumental results indicated a high level of PAHs in the extracts, which could lead to super induction of the aryl hydrocarbon receptor (AhR) and therefore, to a positive bias in the results. Instrumental screening proved that all selected preparatory protocols were inadequate at removing interfering compounds and not sufficiently selective for PCDD/Fs, although the TRP was more successful in removing interferences. The high matrix interference hindered peak identification. Additionally, as indicated by instrumental analysis, the weak recovery of PCDD/Fs could be ascribed to high evaporation temperatures. The effect of different reference standards in the H4IIE bio-assay used during semi-quantification needs further investigation; similarly, the optimisation of extraction, evaporation and clean-up protocols and the use of different GCxGC-TOFMS column combinations aimed at more efficient separation needs to be investigated. The assistance of the National Metrology Institute (funded through the Department of Trade and Industry) towards this research is hereby acknowledged. / Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2013.

Concern on a global scale gave rise to the founding of the Stockholm Convention on persistent organic pollutants (POPs) with a view to restrict the use and production of these toxic chemicals. As a signatory, South Africa is legally bound to abide to the Convention’s objectives, including participating in relevant research and monitoring. However, developing countries such as South Africa have limited information concerning POPs, partially because these countries do not have sufficient analytical capabilities, and thus method development and refinement are necessary. One group of POPs consisting of polychlorinated dibenzo-pdioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs), collectively referred to as dioxins, are of particular concern due to their high toxicity and persistence. Additionally, the analysis of dioxins is recognised as one of the most analytically challenging of its kind. This study investigated the effect of different preparatory protocols on the semi-quantification of dioxins using the H4IIE-luc-reporter gene assay. The protocols evaluated were either Soxhlet or pressurised liquid extraction (PLE) combined with a manual acid digestion, gel permeation chromatography (GPC) and Florisil fractionation clean-up procedure as well as the automated Total Rapid Prep™(TRP) system which makes use of a PLE combined with a multi-layer silica, alumina and carbon column clean-up procedure. To evaluate the protocols, an eight point matrix matched calibration curve, two soil samples and a certified reference material (CRM) were used. The extracts were semi-quantified by the H4IIE-luc bio-assay. During the course of the assay, the appropriateness of different standards was investigated, and a mixed standard containing all 17 toxic PCDD/Fs was chosen for quantification. During the data review process, higher bioassay equivalent (BEQ) values were obtained from PLE compared to Soxhlet extraction, while no statistically significant difference (Kruskal-Wallis ANOVA: p > 0.05) was found between the assay quantifications for the different preparatory techniques. However, the results of the H4IIE bio-assay were larger than the expected values. The identity of the chemicals that were in all likelihood responsible for the higher response was investigated through instrumental analysis using comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GCxGC-TOFMS). Instrumental results indicated a high level of PAHs in the extracts, which could lead to super induction of the aryl hydrocarbon receptor (AhR) and therefore, to a positive bias in the results. Instrumental screening proved that all selected preparatory protocols were inadequate at removing interfering compounds and not sufficiently selective for PCDD/Fs, although the TRP was more successful in removing interferences. The high matrix interference hindered peak identification. Additionally, as indicated by instrumental analysis, the weak recovery of PCDD/Fs could be ascribed to high evaporation temperatures. The effect of different reference standards in the H4IIE bio-assay used during semi-quantification needs further investigation; similarly, the optimisation of extraction, evaporation and clean-up protocols and the use of different GCxGC-TOFMS column combinations aimed at more efficient separation needs to be investigated. The assistance of the National Metrology Institute (funded through the Department of Trade and Industry) towards this research is hereby acknowledged. / Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2013.

Baltic archipelago areas have high nature values despite being polluted from various antrophogenic activities within the Baltic Sea catchment area and from long-range transport of airborne substances. The discovery of environmental problems in the Baltic Sea in the 1960s led to countermeasures that gradually gave results in reducing the toxic pollution, e.g. from PCBs. Today, much of the environmental management is focused on reducing the effects of eutrophication. There is a demand from society on science to develop strategies that can direct remedial actions so that the cost-effectiveness is maximised. This work focuses on how mass-balance models can be used to understand how coastal ecosystems are controlled by abiotic processes and to predict the response to changes in loading of different substances. Advection, sedimentation and burial are examples of general transport processes that are regulated by morphometrical characteristics, e.g. size, form, effective fetch and topographical openness. This is why different coastal areas have different sensitivity to loading of pollutants. A comparison of six phosphorus and chlorophyll models of different complexity showed that the model performance was not improved with more state variables of total phosphorus (TP) than two water and two sediment compartments. Modelling chlorophyll as a separate state variable did not improve the results for individual values compared to a simple regression against total phosphorus in surface water. Field investigations of the phosphorus content in accumulation sediments along the coast of Svealand showed a distribution pattern that probably is related to differences in the redox status. The average content of mobile phosphorus was much higher than previously found in offshore Baltic sediments indicating that sediments may play an important role for the phosphorus turnover in Baltic archipelago areas. A one-year field study to measure the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in water, sediments and fish during different seasons was carried out in Kallrigafjärden Bay. The collected data set was used to test a mass-balance model for PCCD/F-turnover. It was possible to reproduce the concentrations of different PCDD/F-congeners with high accuracy using a general model approach, including one water compartment and two sediment compartments, indicating that the applied model has the necessary qualifications for successful predictions of PCDD/F-turnover in Baltic coastal areas. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 736

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.

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.

D.L. A 792-2008 / Ministerio de Educación y Ciencia; Programa FEDER; Generalitat Valenciana; Universidad de Alicante.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans(PCDFs) are two groups of lipophilic, persistent organic pollutants that are produced as by-products of various anthropogenic and industrial processes. Due to their relatively high toxic potencies and potential to bioaccumulate and biomagnify in organisms and through the food chain, the contemporary widespread distribution of these compounds is a concern to the health of the environment, wildlife and humans. This study determined the distribution, pathways and fate of PCDD/Fs in the coastal zone of Queensland, Australia, including the inshore marine environment of the World Heritage Great Barrier Reef Marine Park. This ecosystem supports unique fauna and flora such as the marine herbivorous mammal dugong (Dugong dugon) and its food source, seagrass. Elevated PCDD/Fs were present in soils and sediments along the entire Queensland coastline. Highest concentrations were found in soil from agricultural irrigation drains and in sediments near the mouths of major rivers. Elevated concentrations were associated with rural and urban types of land-use, and PCDD/Fs were present even in locations remote from anthropogenic activities. PCDD/F congener-specific analysis revealed an unusual profile in all samples, dominated by OCDD, with PCDFs present in low concentrations or below the limit of detection. Distinct HxCDD isomer patterns were observed, with the 1,2,3,7,8,9-HxCDD/1,2,3,4,6,7-HxCDD isomer pair dominating the 2,3,7,8-substituted HxCDDs. Similar congener and isomer characteristics were reported in sediments, soil and clay samples from other continents, but could not be attributed to any known source. Possible PCDD/F sources in Queensland were assessed using segmented estuarine sediment cores, for which radiochemical chronologies were established for each depth. Variations of PCDD/F concentrations in the sediment cores over several centuries of depositional history were relatively small. Elevated PCDD levels were still present in sediment slices from the early 17th century. PCDD/F homologue profiles in sediments deposited during the last 350 years were almost identical and correlated well to the characteristic profiles observed in surface sediments and soils from the entire Queensland coastline. These results suggested the presence of an unidentified PCDD source prior to the production of commercial organochlorine products. To investigate the formation of the unusual PCDD/F profiles, congener and isomer specific analyses were undertaken in soils, sediments and dated sediment cores. The results demonstrated that specific transformation processes in the environment have resulted in the observed PCDD profile characteristics. Dechlorination of OCDD was proposed to result in distinct 1,4-pattern characteristics (i.e. formation of isomers chlorinated in the 1,4,6,9-positions). Consequently, the environmental samples do not reflect the signatures of the original source. An alternative hypothesis to natural formation is discussed evaluating these processes and their implications for possible source contributions. This hypothesis explores the potential for the influence of anthropogenic PCDD precursors (e.g. pentachlorophenol) during the 1940s to 1990s. Transport of PCDD/Fs from the land-based source via impacted tributary river systems, and subsequent deposition processes are proposed to result in PCDD/F accumulation in the inshore marine ecosystem. The extent of the sediment PCDD/F contamination governs the concentrations in the extensive inshore marine seagrass meadows of Queensland. Partitioning processes in the sediment-seagrass system lead to increased toxic equivalency (TEQ) in the seagrass, compared to sediment.The relationship between contaminated inshore sediments, seagrass and dugongs were evaluated using six dugong habitat regions along the coastline. PCDD/F body burdens in dugongs are governed by sediment (and seagrass) PCDD/F concentrations in their habitat. High seagrass (and incidental sediment) ingestion rates, selective retention of toxicologically potent congeners and relatively low PCDD/F elimination capacities in dugongs are proposed to result in elevated PCDD/F concentrations and TEQ levels in adult animals. Transfer efficiencies of 4 and 27% of maternal TEQ levels to foetuses and calves (respectively) during gestation and lactation result in relatively high exposure potentials to offspring. Compared to no-observed-adverse-effect-levels in other mammals, and based on the results of this study, a tolerable daily intake (TDI) of 10-24 pg TEQ kg-1 day-1 was estimated for dugongs. The results of the present study found that dugongs from some regions along the coastline of Queensland exceed this TDI by up to 20 fold, suggesting that these populations may be at risk from PCDD/F contamination in their habitat. These results have important implications for the health of the environment, wildlife and humans and were used to develop a conceptual understanding of the sources, pathways and fate of dioxins in Queensland, Australia.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are by-products emitted from combustion sources such as municipal solid waste (MSW) incineration plants. These organic compounds are recognized as toxic, bioaccumulative and persistent in the environment. PCDD/Fs are removed from flue gases before released from MSW incineration. However, the PCDD/Fs are not destroyed but retained in the residues, thus in the environment. Understanding the pathways that lead to their formation is important in order to develop ways to suppress their formation and prevent their release into the environment. Suppressing the formation can also allow less expensive air pollution control system to be used, and/or the costs of thermally treating the residues to be reduced. The main objective of the studies underlying this thesis was to elucidate process, combustion and fuel parameters that substantially affect the emission levels and formation of PCDD/Fs in flue gases from MSW incineration. The experiments were conducted under controllable, realistic combustion conditions using a laboratory-scale reactor combusting artificial MSW. The parameter found to most strongly reduce the PCDD/F emissions, was prolonging the flue gas residence time at a relatively high temperature (460°C). Increasing the sulfur dioxide (SO2) to hydrogen chloride (HCl) ratio to 1.6 in the flue gas was also found to reduce the PCDF levels, but not the PCDD levels. Fluctuations in the combustion process (carbon monoxide peaks), high chlorine levels in the waste (1.7%) and low temperatures in the secondary combustion zone (660°C) all tended to increase the emission levels. The PCDD/PCDF ratio in the flue gas was found to depend on the chlorine level in the waste, fluctuations in the combustion process and the SO2:HCl ratio in the flue gas. The formation pathways were found to be affected by the quench time profiles in the post-combustion zone, fluctuations in the combustion process and addition of sulfur. In addition, increased levels of chlorine in the waste increased the chlorination degrees of both PCDDs and PCDFs. A tendency for increased SO2 levels in the flue gas to increase levels of polychlorinated dibenzothiophenes (sulfur analogues of PCDFs) was also detected, however the increases were much less significant than the reduction in PCDF levels.