Persistent organic pollutants (POPs) are a threat to the environment and human health because they are ubiquitous, resistant to degradation, can bio-accumulate in organisms and bio-magnify in food chains. They have a detrimental effect on the reproductive, nervous and immunity systems of vertebrates. An international treaty, the Stockholm Convention on POPs, came into force in 2004 and aims to limit and eventually prohibit any use and unintentional production of POPs. South Africa ratified the Convention in 2002. Those compounds currently listed by the Stockholm Convention as POPs include chlorinated pesticides such as dichlorodiphenyltrichlorethane (DDT), chlordane and dieldrin, and industry-related compounds such as polychlorinated biphenyls (PCBs) and hexachlorobenzene. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are also regarded as POPs but - together with some PCBs - they are the unintentional result of anthropogenic activity. This study focussed on the PCDDs, PCDFs and dioxin-like PCBs in the aquatic environment of South Africa particularly because the water resources in this country are under pressure. Despite the fact that South Africa has the sources of these compounds, little is known about the levels of these three groups of compounds. The concentration of twelve dioxin-like PCBs, seven PCDDs and ten PCDFs were determined for 22 sites selected on the grounds of their proximity to possible pollution sources. Analytical determinations included gas chromatography/mass spectrometry and a cell-based bio-assay, the H4IIE-/17C reporter gene assay. Possible sources of the observed pollution were inferred using the following statistical investigative methods: principal component and hierarchical cluster analysis. Seven of the sites had levels higher than the threshold effect concentration of Canada's sediment quality guidelines of 0.85 ngTEQ kg'1 (Toxic Equivalency Quotient). The other sites had lower levels. The highest concentration, 17.8 ng TEQ kg"1, was measured at a site in the southern Gauteng Province. Most of the PCDD/F pollution seemed to have come from combustion sources related to human activity, rather than industrial combustion. Most of the dioxin-like PCB pollution seemed to have been from commercial PCB preparations. Future research would require better characterisation of the sources in order to reduce the formation of these compounds, but also to better understand the exposure and risk scenarios, if humans are to be in close contact with these sources. / Thesis (Ph.D. (Zoology))--North-West University, Potchefstroom Campus, 2008.

ABSTRACT The tropical and subtropical nearshore marine environments of Queensland, Australia sustain diverse and unique marine wildlife. Continuous population growth and land-use changes along the Queensland coastline are known to exert numerous anthropogenic pressures on these marine ecosystems, including the delivery of high sediment loads. Sediments also provide a transport pathway for persistent organic pollutants (POPs) from rural and urban catchments into the marine environment. While such pollutants are known to be elevated in marine sediment and biota from nearshore areas in Queensland, their input and distribution pathways, as well as exposure and associated risks to wildlife populations are only partially understood. Mounting evidence suggests that POPs may contribute to population declines in marine wildlife species; however, limited information is available regarding the accumulation and effects of these contaminants in endangered or threatened marine turtles. This study aimed to redress some of these information gaps using a case study approach in marine turtle habitats of Moreton Bay, and other embayments in Queensland. Among persistent organic pollutants (POPs), dioxins (polychlorinated dibenzo-p-dioxins; PCDDs) and to some extent also dioxin-like PCBs (polychlorinated biphenyls; PCBs) were found to be widespread and often present at elevated (ppb) levels in surface sediments from Moreton Bay. However, while PCDD/F toxic equivalencies (TEQs) are above international (Canadian) sediment quality guidelines at numerous sites in Moreton Bay, in general TEQs across the Bay are relatively low compared to those from contaminated locations near dense industrial activities. POP contamination in surface sediments across Moreton Bay was investigated by a combination of GIS spatial mapping, geostatistical and traditional statistical modalities. High spatial variability and complex spatial distribution patterns were revealed. High resolution GIS kriging model outputs from the mid to southern Bay facilitated identification of distinct sediment contamination zones, with highest PCB and PCDD/F levels present in nearshore locations, associated with nearby river systems. While primarily governed by organic carbon, a multitude of physical, chemical and hydrological factors were identified to influence the spatial variance of PCDD/F concentrations. The main parameters governing PCDD/F spatial distribution were identified as sediment geochemistry, water depth and anthropogenic alterations of the physical environment and, together, all quantifiable explanatory variables (including hydrodynamic flushing) explained ≈75% of spatial PCDD/F variance. Together, the interaction of these parameters results in complex distribution patterns and highly variable concentrations even among neighbouring sites of 1-3 km resolution. These results suggest that prediction models of POP distributions in the nearshore marine environment may require high-resolution validation, and highlights that the design of low resolution monitoring strategies can have profound impacts on the reliability of contaminant information or any subsequent extrapolations. This knowledge and methodology can be utilised to optimise on-going and future near-shore sediment monitoring programs both locally and in other regions around the world. Using the spatial distributions of dioxin-like contaminants within sediments, this study provided an opportunity to assess field-based relationships between habitat contamination and local marine biota contamination. Detectable levels of PCDD/Fs and dioxin-like PCBs were measured in all green, hawksbill, loggerhead and flatback marine turtle tissues. POP concentrations in sediments were found to significantly correlate with those in the herbivorous green turtle from different sediment contamination zones. These findings demonstrate that sediments represent an important secondary contaminant source and lead to redistribution of POPs to the marine food chain. POP concentrations and TEQs clearly increased from sediment to turtles as well as with increasing trophic levels in marine turtle species. The results from this study demonstrate that the extent of sediment contamination within foraging habitats governs marine turtle exposure, while, trophic status and to some extent age influence contaminant exposure within a particular contamination zone. Despite the relatively low TEQ in sediments from Moreton Bay, TEQ levels in green turtle sub-populations foraging from near-shore locations and higher trophic loggerhead and flatback turtles are similar or elevated compared to those reported for other marine wildlife from Moreton Bay and elsewhere, even compared to higher trophic species from locations impacted by dense industrial activities. High bioaccumulation potential of 2,3,7,8-PCDD/F and dioxin-like PCBs compounds were estimated for green turtles using biota to sediment accumulation factors. Selective accumulation of toxicologically more potent (i.e. lower chlorinated) PCDD/Fs was observed for higher trophic marine turtles, resulting in increasing TEQs for the carnivorous species. Biomagnification was also observed for some non-2,3,7,8-substituted dioxin congeners which typically do not accumulate in most biota. These results are proposed to be due to relatively high accumulation efficiency and/or low metabolic capacity for these POP compounds in marine turtles. These findings are also hypothesised to reflect temperature dependant, greater bioavailability of hydrophobic chemicals in sub-tropical and shallow marine systems. An additional pilot study revealed that in contrast to PCDD/Fs and PCBs, levels of persistent flame retardants (polybrominated diphenyl ethers; PBDEs) were relatively low in marine turtles and other marine species (dugong, fish and shellfish) from Moreton Bay. This suggests relatively low level input of these more recent industrial products into the marine environment. However, as elevated levels of PBDEs have been reported in blood from the general population of Australia, ongoing transport from the terrestrial to the marine system and redistribution of these contaminants, similar to PCDD/F and PCBs, would be expected to occur into the future. Limited information is available regarding the sensitivity of reptiles to and effects of POPs, however, studies have shown that reptiles are sensitive to POPs albeit with uncharacterised relative potency. In the absence of robust toxicological information for reptiles or marine turtles, the potential risks associated with PCDD/F and PCB exposure of Queensland turtle populations was evaluated using toxicity for sensitive biological endpoints observed in mammals and birds. Using probabilistic methodology for marine turtles from Queensland, the body burden of up to 31% and 55% of green and loggerhead turtles, respectively, are above the threshold levels where the most sensitive physiological effects are observed in mammals and birds. While this evaluation illustrates that the contaminants investigated have the potential to impact on the health of marine turtle populations, it must be highlighted that it is compromised by the lack of species-specific (and in this case, class-specific) information, the uncertainty of which is often considered to represent a factor of at least 10. The findings of the present study indicate that exposure to POPs has the potential to adversely affect the health of Queensland’s marine turtle populations, and highlight the need for robust information on reptile specific sensitivity to these compounds.

Polychlorinated-p-dibenzo dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) (collectively termed ‘dioxins’) and polychlorinated biphenyls (PCBs) are three groups of persistent organic pollutants (POPs) ubiquitous in the environment due to their emission from numerous sources, high persistency and a propensity to be transported long distances. These compounds bioaccumulate in animal tissue, biomagnify through the food web and are toxic to humans and wildlife at relatively low concentrations. Humans may be exposed to POPs via ingestion, inhalation and dermal absorption, however, for the general population, approximately 90% of the total exposure occurs through intake of contaminated food particularly from lipid rich products, including seafood. An Australian national study highlighted that, similar to many other countries, seafood contributes a major proportion to dioxin and PCB exposure of Australians. As typical for national studies, the exposure assessment utilised contaminant concentrations in retail (sea)food and consumption information based on national dietary surveys. The risk assessment showed that the Australian population on the whole has a very low risk of exposure to dioxins through food. However, more than 80% of the Australian population lives within 50 km of the coast, where recreational, cultural and/or subsistence fishing of local seafood is prominent, potentially from areas with elevated PCDD/F and PCB concentrations. Through analysis of local seafood contamination and community seafood consumption patterns, this study assessed PCDD/F and PCB exposure for a coastal subpopulation in Moreton Bay, Queensland who consume locally caught seafood from an area with elevated PCDD/F and PCB concentrations but relatively low (background) toxic equivalency (TEQDP) in sediments, which is typical for Australian nearshore marine systems. Despite low sediment TEQDP levels, due to the dominance of octachlorodibenzo-p-dioxin (which is considered less potent compared to the most toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin), elevated TEQDP concentrations were present in local seafood. In particular higher trophic fish species and some traditional seafood were found to contain TEQDP above current EU action and maximum limits. This highlights the efficiency of species specific contaminant uptake, bioaccumulation and biomagnification processes, which can result in accumulation of higher toxic dioxin and PCB congeners in biota. In contrast, concentrations of most organochlorine pesticides and flame retardants (polybrominated diphenylehters (PBDEs)) were relatively low in seafood from Moreton Bay. For fish, uptake of highly lipophilic contaminants, such as PCDD/Fs and PCBs occurs predominantly via food (biomagnification) and respiratory processes (bioconcentration) followed by selective accumulation of the more toxic, lower chlorinated 2,3,7,8 PCDD/F congeners. This study discovered that physical contact with sediment and dermal absorption of lipophilic contaminants also represents an important exposure pathway for sediment dwelling fish, resulting in higher lipid normalised PCDD/F, PCB and TEQ levels (up to 8, 5 and 3 fold) in skin compared to muscle tissue. PCDD/F and PCB congener profiles differed between muscle and skin suggesting biomagnification and skin absorption as the respective predominant uptake pathways for these tissues. Dermal uptake was estimated to contribute up to 46% to the total TEQDP load on a lipid basis in sediment dwelling fish species, thus representing an important exposure pathway, and extending the bioavailability of sediment-sorbed pollutants to the food web. Accurate determinations of lipid content and lipid TEQDP contamination within seafood samples are critical to human exposure assessments. To ensure quality assurance, different seafood extraction methods were tested to evaluate their impact on lipid yields and contaminant concentration. While levels of PCDD/Fs and PCBs on a lipid basis did not vary across the different methods employed in this study, sample preparation is a significant determinant of lipid yield from fattier fish species. If samples were freeze dried prior to extraction, 30% higher TEQDP values (on a wet weight basis) were obtained as compared to extraction using fresh sample material. Such variance in lipid results will have a significant impact on exposure assessments and should be taken into consideration during seafood contaminant analysis. The median TEQDP concentration from local seafood was approximately 25 fold higher compared to the retail seafood analysed for the national Australian risk assessment. The seafood consumption survey results from this study further indicate that coastal subpopulations consume considerably more seafood than the general population (2 to 6 times more in the present case study). This proved to be an important driver for contaminant exposure in this subpopulation. The average monthly dioxin intake for the coastal community ranged between 34 (best case) to 107 (worst case) pg TEQ kg bw-1 month1, (95th percentile: 114 - 362 pg TEQ kg bw-1 month1), an order of magnitude higher than that estimated for the general population. The contaminant exposure via the local seafood consumption pathway alone exceeded WHO tolerable daily intake levels in 11-44% of the population. These results have important implications with respect to adequate contaminant exposure assessments of Australian and other coastal subpopulations. The study outcomes highlight the importance of considering local conditions and information on contaminant fate processes for human exposure evaluations. Local seafood consumption in coastal communities can result in high exposure to PCDD/F and PCBs, even in background contamination areas. This information would be important to consider for developing future sediment quality guidelines and with respect to exposure and associated risks for coastal communities in general.

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>

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.

En la present tesi doctoral s’han estudiat diversos mètodes per a l’eliminació de contaminants orgànics persistents en olis de peix amb finalitat alimentària. S’han posat al punt les metodologies d’anàlisi necessàries per a la correcta determinació d’aquests compostos en la matriu d’estudi. S’han avaluat amb detall les etapes de purificació de la mostra, fraccionament dels analits i anàlisi instrumental. El mètode ha estat validat amb resultats satisfactoris, i s’ha comprovat el seu bon funcionament a través de la participació en diversos exercicis d’intercalibtage, així com la realització de diversos estudis amb mostres reals d’oli de peix. S’ha estudiat l’eliminació dels contaminants orgànics persistents a través d’adsorbents sòlids amb base silícica i carbonàcia. Les condicions experimentals han estat estudiades més a fons mitjançant dissenys d’experiències, per acabar optimitzant el mètode d’adsorció amb un disseny d’evolució. Els millors resultats s’han obtingut amb el carbó actiu, que mostra una elevada eficàcia en l’eliminació de PCDD/Fs, d-l PCBs i HCB. S’ha estudiat l’eliminació dels contaminants orgànics persistents mitjançant tècniques de degradació fotoquímiques. Inicialment s’ha fotodegradat cada família de contaminants per separat, per poder estudiar més a fons les condicions necessàries per la seva eliminació, així com els seus mecanismes i productes de degradació. Posteriorment s’ha estudiat la fotodegradació simultània dels analits d’interès en oli de peix. Aquesta tècnica s’ha mostrat efectiva en l’eliminació de DDT, PBDEs, HCB i PCBs similars a dioxines. Paral•lelament als estudis d’eliminació mitjançant adsorbents sòlids i tècniques fotoquímiques, s’ha comprovat la qualitat dels olis de peix abans i després del tractament. El procés d’adsorció en sòlids no afecta significativament a la qualitat de l’oli, mentre que les tècniques fotoquímiques degraden una part dels àcids grassos insaturats. S’ha estudiat l’eliminació de contaminants orgànics persistents en oli de peix mitjançant la combinació de les dues tècniques estudiades anteriorment, amb una primera etapa de degradació fotoquímica i una segona etapa d’adsorció. S’han comparat els resultats finals d’eliminació que s’obtenen amb cada un dels mètodes desenvolupats (adsorció, fotodegradació i combinat). L’adsorció en carbó actiu és el procés més adequat per l’eliminació de COPs en oli de peix. S’ha realitzat un estudi dels nivells diastereomèrics i enantiomèrics d’un contaminant emergent -l’hexabromociclododecà (HBCD)- en oli de peix. S’ha avaluat la seva eliminació de la matriu d’estudi mitjançant adsorbents amb base carbonàcia i degradació fotoquímica, sent principalment eliminat per aquesta segona via. / En la presente tesis doctoral se han estudiado diversos métodos para la eliminación de contaminantes orgánicos persistentes en aceites de pescado con finalidad alimentaria. Se han desarrollado los métodos de análisis necesarios para la correcta determinación de estos compuestos en la matriz de estudio. Se han evaluado con detalle las etapas de purificación de la muestra, fraccionamiento de los analitos y análisis instrumental. El método ha sido validado con resultados satisfactorios, y se ha comprobado su buen funcionamiento mediante ejercicios de intercalibraje, así como la realización de diversos estudios con muestras reales de aceite de pescado. Se ha estudiado la eliminación de los contaminantes persistentes mediante adsorbentes sólidos con base silícica y carbonacea. Las condiciones experimentales han estado estudiadas en profundidad mediante diseños de experiencias y de evolución. Los mejores resultados se han obtenido con carbón activo, que demuestra una elevada eficacia en la eliminación de PCDD/Fs, dl-PCBs y HCB. Se ha estudiado la eliminación de los contaminantes orgánicos persistentes mediante técnicas de degradación fotoquímica. Inicialmente se ha fotodegradado cada familia de contaminantes por separado, para poder estudiar más a fondo las condiciones necesarias para su eliminación. Posteriormente se ha estudiado la degradación simultánea de los analitos de interés en aceite de pescado. Esta técnica se ha mostrado efectiva en la eliminación de DDT, PBDEs, HCB y PCBs similares a dioxinas. Paralelamente a los estudios de eliminación mediante adsorbentes sólidos y técnicas fotoquímicas, se ha comprobado la calidad de los aceites de pescado antes y después del tratamiento. El proceso de adsorción en sólidos no afecta significativamente a la calidad del aceite, mientras que las técnicas fotoquímicas degradan una parte de los ácidos grasos insaturados. Se ha estudiado la eliminación de contaminantes orgánicos persistentes en aceites de pescado mediante la combinación de las dos técnicas estudiadas anteriormente, con una primera etapa de degradación fotoquímica y una segunda etapa de adsorción. Se han comparado los resultados finales de eliminación que se obtienen con cada uno de los métodos desarrollados. La adsorción en carbón activo es el proceso más adecuado para la eliminación de COPs en aceite de pescado. Se ha realizado un estudio de los niveles diastereoisoméricos y enantioméricos de un contaminante emergente –HBCD- en aceite de pescado. Se ha evaluado su capacidad de eliminación de la matriz de estudio mediante adsorbentes con base carbonacia y degradación fotoquímica, siendo principalmente eliminado por la segunda vía. / During the present doctoral thesis several methods for the elimination of persistent organic pollutants from fish oil have been studied. Analytical methodologies for the determination of these compounds in fish oil have been developed. Sample purification, fractionation of the analytes and instrumental determination steps have been deeply studied. The method has been validated with satisfactory results, and its performance has been verified through its participation in several intercalibration exercises and studies with real fish oil samples. Elimination of persistent organic pollutants with silicon and carbon-based adsorbents has been studied. The experimental conditions have been studied in depth with an experimental design, to finally optimize the adsorption method using an evolutionary design. Best results have been obtained with the active carbon, showing high efficiency of the removal of PCDD/Fs, dioxin-like PCBs and HCB. Elimination of persistent organic pollutants with photochemical degradation techniques has been studied. Initially, each family of pollutants has been photodegraded separately, to determine its degradation conditions, as well as degradation mechanisms and by-products. Later, simultaneous photodegradation of the analytes has been studied in fish oil. This technique has shown high efficiency on the degradation of DDT, PBDEs, HCB and dioxin-like PCBs. The quality of the oils before and after the treatments with solid adsorbents and photochemical degradation has also been studied. The adsorption process does not significantly affect the quality of the oils, while photochemical techniques can degrade the unsaturated fatty acids. Elimination of persistent organic pollutants in fish oil combining adsorption in solids and photochemical degradation has been studied. Results obtained with each of the developed methodologies (adsorption, photodegradation and combined method) were compared. Adsorption in active carbon is the most suitable process for COPs elimination in fish oil. Finally, diastereoisomeric and enantiomeric levels of an emerging pollutant –hexabromocyclododecane (HBCD)- in fish oil have been studied. Its elimination has been evaluated with carbon-based adsorbents and photochemical degradation, being mainly eliminated with the photodegradation techniques.

The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition. The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation. In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.