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.

POPs are a group of chemicals that have been extensively studied over the last few years. The main reason that these chemicals have received so much scientific attention is the myriad of negative effects they have on the environment and human health. The properties that cause the deleterious effects include a high molecular stability, rendering them highly persistent. Added to this is the lipophilic and hydrophobic nature of the compounds. POPs will thus tend to bio-accumulate and bio-magnify in the environment, causing a direct threat to humans and wildlife. To address this threat, the Stockholm Convention on Persistent Organic Pollutants, under the supervision of United Nations Environment programme (UNEP), was initiated and became legally binding on 17 May 2004. All countries, including South Africa, which ratified this agreement, will be expected to monitor and regulate the formation of POPs. Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are all members of the dioxin-like family of POPs. This family of chemicals pose serious health threats such as carcinogenic effects and negative effects on reproduction. These substances, with the exception of PCBs, are formed unintentionally as by-products of industrial and thermal processes. One of the main sources of dioxin-like chemicals is medical waste incinerators. In this project the area surrounding a medical waste incinerator was monitored using a bio-assay technique. The determination of dioxin concentrations is usually preformed by chemical analysis, however, bio-assays have proven themselves to be a cheaper and time-saving screening method. The Toxic Equivalency Quotient (TEQs) determined through bio-assays can support chemical analysis in determining biologically-relevant risk assessments since bio-assay data has ecotoxicological relevance. These assays represent an integrated biological response to chemical pollutants, where biological effects are accounted for which is not possible in chemical analyses. One of the bio-assays used in the determination of the dioxin-like chemical TEQ is the H411 E reporter gene bio-assay. This assay is based on the Ah-receptor mediated toxicity of dioxin-like chemicals. Using this technique the TEQs for areas surrounding an active incinerator were determined, to indicate the distribution of these substances. The TEQs for the soil samples collected ranged between nondetectable and 154 ngTEQ/kg. There was no clear distributional pattern and the total organic carbon content in the soil did not seem to play a crucial role in the distribution of dioxin-like chemicals. Although a decrease in soil tillage showed a corresponding increase in TEQ. The predominant wind direction was taken into account but no correlation could be seen. However, meteorological parameters such as the ambient temperature and low precipitation in the area may have contributed to lower TEQ values. Cytotoxicity excluded data points and the phenomenon has to be addressed. High TEQ values in a residential area where free-range chickens are raised pose a serious concern to the level of dietary dioxin-like chemical intake. Eggs in the area could theoretically contain between 2.75 and 28.75 pgTEQ/g egg fat. Further studies are needed to determine how much dioxin-like chemicals are being transferred to humans through the consumption of free-range eggs / Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2006.

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.

<p>Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzo-furans (PCDFs) belong to the most toxic compounds known to science and they are defined as Persistent Organic Pollutants (POPs) under the Stock-holm Convention. The general human exposure to PCDD/Fs is primarily through dietary intake. The importance of contaminated sites as secondary PCDD/F sources (i.e. sources that once received its contamination from a primary source) are getting increased attention. To be able to assess the risks for human exposure at PCDD/F contaminated sites, the environmen-tal distribution of PCDD/Fs and the potential mobilization between dif-ferent environmental media (e.g. food chain transfer) must be known. The primary aim of the work presented in this thesis was to investigate human exposure pathways associated with PCDD/F contaminated sites by combining field measurements and modeling. Site specific field measurements were made at a PCDD/F contaminated site in Sweden and multimedia modeling scenarios were evaluated against site specific data and national reference data.</p><p>The results show that the congener distributions in exposure media affected by contaminated soil may differ significantly from the distribu-tions found in media from reference locations. Higher chlorinated PCDD/Fs may be transferred into food chains where they contribute to a large fraction of the toxic equivalent concentration (TEQ). Ingestion of locally produced animal food may be an important exposure pathway al-ready at low or moderate PCDD/F soil concentrations. However, the con-gener composition of the source is critical for the exposure. The signifi-cance of the individual exposure routes varies depending on e.g. the spatial distribution and magnitude of the soil contamination, the pro-perties of the exposure media and the human behavior. Multimedia mo-deling can be used in risk assessments as long as model algorithms and model parameters are representative for the superhydrophobic properties of PCDD/Fs. However, selection of physical-chemical PCDD/F properties is a challenge due to large variation in reported values. For some proper-ties, data is scattered or completely lacking</p>

Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzo-furans (PCDFs) belong to the most toxic compounds known to science and they are defined as Persistent Organic Pollutants (POPs) under the Stock-holm Convention. The general human exposure to PCDD/Fs is primarily through dietary intake. The importance of contaminated sites as secondary PCDD/F sources (i.e. sources that once received its contamination from a primary source) are getting increased attention. To be able to assess the risks for human exposure at PCDD/F contaminated sites, the environmen-tal distribution of PCDD/Fs and the potential mobilization between dif-ferent environmental media (e.g. food chain transfer) must be known. The primary aim of the work presented in this thesis was to investigate human exposure pathways associated with PCDD/F contaminated sites by combining field measurements and modeling. Site specific field measurements were made at a PCDD/F contaminated site in Sweden and multimedia modeling scenarios were evaluated against site specific data and national reference data. The results show that the congener distributions in exposure media affected by contaminated soil may differ significantly from the distribu-tions found in media from reference locations. Higher chlorinated PCDD/Fs may be transferred into food chains where they contribute to a large fraction of the toxic equivalent concentration (TEQ). Ingestion of locally produced animal food may be an important exposure pathway al-ready at low or moderate PCDD/F soil concentrations. However, the con-gener composition of the source is critical for the exposure. The signifi-cance of the individual exposure routes varies depending on e.g. the spatial distribution and magnitude of the soil contamination, the pro-perties of the exposure media and the human behavior. Multimedia mo-deling can be used in risk assessments as long as model algorithms and model parameters are representative for the superhydrophobic properties of PCDD/Fs. However, selection of physical-chemical PCDD/F properties is a challenge due to large variation in reported values. For some proper-ties, data is scattered or completely lacking

Abstract In Finland there is a food monitoring program which has found elevated dioxin and polychlorinated biphenyl concentrations in the muscle of semi-domesticated reindeer (Rangifer tarandus tarandus) calves. This led to further research on the concentrations of persistent organic pollutants in reindeer muscle, liver, and other internal organs. The research was further expanded on wild moose (Alces alces) muscle and liver. The main objective of this thesis is to increase knowledge of polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), polychlorinated biphenyl (PCB), and polybrominated diphenyl ether (PBDE) pollution levels in the Finnish terrestrial environment, and in semi-domesticated reindeer and wild moose in particular. The research gives information of exposure conditions in the reindeer’s food chain, as well as species differences and individual variation in accumulation and distribution of pollutants in reindeer and moose. Local differences between the contaminant concentrations were explored. Toxic equivalencies (TEQs) set by the World Health Organization (WHO) of PCDD/Fs and PCBs were calculated in order to assess the validity of selling reindeer and moose tissue. It was observed that there is a species-, individual-, and tissue-specific accumulation of dioxins, dioxin-like PCB, and PBDE compounds in reindeer and moose. Varying exposure conditions mainly explain the differences, although taking into account the age of an individual animal, its metabolic patterns have a role, too. Reindeer placenta and milk proved to be important factors in the transporting of compounds from hind to calf. The highest PCDD/F and PCB concentrations (as WHO-TEQs) were observed in reindeer calves in the study area in which animals are fed in natural pastures only. Despite the findings, it was concluded that it is safe to eat reindeer and moose meat since the concentrations of dioxins and dioxin-like PCBs in the muscle are relatively low, and because of the low fat content in these animals. Reindeer liver, for its part, had quite a lot of dioxin-like compounds that may compromise its safety as food, at least on a regular basis. The study shows that Finnish semi-domesticated reindeer and wild moose are good indicator species of POP contamination in a terrestrial environment, reindeer describing the situation in northern parts of the country especially. / Tiivistelmä Suomalaisessa ruokamonitorointitutkimuksessa löydettiin kohonneita dioksiinien ja polykloorattujen bifenyylien pitoisuuksia puolivillin poron vasojen lihaksista. Se johti lisätutkimuksiin pysyvien orgaanisten yhdisteiden pitoisuuksista poron lihaksessa, maksassa ja muissa sisäelimissä. Tutkimus laajeni koskemaan myös hirven (Alces alces) lihasta ja maksaa. Väitöskirjatyö lisää tietämystä polykloorattujen dibentso-p-dioksiinien (PCDD), polykloorattujen dibentsofuraanien (PCDF), polykloorattujen bifenyylien (PCB) ja polybromattujen difenyylieettereiden (PBDE) pitoisuuksista suomalaisessa maaympäristössä ja erityisesti porossa ja hirvessä. Tutkimus antaa tietoa yhdisteille altistumisesta sekä viitteitä lajien- ja yksilöiden välisistä eroavai¬suuksista yhdisteiden kertymisessä ja niiden jakaantumisessa eri kudosten välillä. Alueellista vaihtelua yhdisteiden pitoisuuksissa selvitettiin myös. Maailman terveysjärjestön (WHO) asettamia PCDD/F- ja PCB-yhdisteiden toksisuusekvivalenttiarvoja (TEQ) tarkasteltaessa pystyttiin arvioimaan kemiallista elintarvikekelpoisuutta suhteessa EU:n antamiin sallittuihin pitoisuuksiin. Työssä havaittiin laji-, yksilö-, ikä- ja kudosspesifistä dioksiinien, dioksiinienkaltaisten PCB- ja PBDE-yhdisteiden kerääntymistä porossa ja hirvessä. Tämä on todennäköisimmin seurausta vaihtelevasta altistumisesta yhdisteille, mutta myös lajien metabolisissa toiminnoissa yksilön eri ikäkausina voi olla eroavaisuuksia. Poron istukan ja maidon havaittiin olevan tärkeitä yhdisteiden kulkeutumisessa emolta sikiölle ja vasalle. Korkeimmat dioksiinien ja dioksiinien kaltaisten PCB-yhdisteiden konsentraatiot (WHO-TEQ-pitoisuuksina) havaittiin poron vasoilla tutkimusalueella, jossa eläimet olivat laiduntaneet ainoastaan luonnonlaitumilla. Huolimatta havaituista haitta-ainepitoisuuksista todettiin, että sekä luonnostaan vähärasvaisen poron että hirvenlihan syönti on turvallista suhteellisen alhaisten dioksiinien ja dioksiininkaltaisten PCB-yhdisteiden pitoisuuksien perusteella. Poron maksa puolestaan sisälsi melko korkeita dioksiinien kaltaisten yhdisteiden pitoisuuksia, mikä voi vaikuttaa sen turvalliseen käyttöön elintarvikkeena ainakin usein syötynä. Suomalainen puolivilli poro ja villi hirvi sopivat hyvin POP-kontaminoitumisen indikaattoreiksi maaympäristössä; poron erityisesti kuvaten tilannetta maan pohjoisosissa.

Modern societies produce large quantities of municipal solid waste (MSW), which is commonly disposed of by incineration. This has several advantages: it reduces the waste’s volume and sterilizes it while also enabling energy recovery. However, MSW incineration has some notable disadvantages, the most widely debated of which is probably the production and release of persistent organic pollutants (POP) such as polychlorinated dibenzofurans (PCDF), dibenzo-p-dioxins (PCDD), biphenyls (PCB) and naphthalenes (PCN). Of the 210 PCDF and PCDD congeners, 17 are toxic, with hormone-disrupting and carcinogenic properties. Twelve of the 209 PCB congeners and at least 2 of the 75 PCN also exhibit such properties. These POP form in the post-combustion zones of MSW incineration plants and are removed from the flue gas using filtering devices that trap them in the fly ash This thesis concerns the formation and degradation of POP in processes related to MSW incineration. The first paper describes a case study in which PCDD were forming in filters designed to remove them from flue gases, causing emission-related issues in a full-scale MSW incineration plant. It was shown that the PCDD formation was probably due to chlorophenol condensation on the filters’ surfaces. The second paper describes the validation of a cooling probe designed to prevent POP formation during high temperature (&gt;450 °C) flue gas sampling. The results obtained also confirmed that PCDF and PCDD formation takes place at temperatures below 600 °C. In the third paper, three different fly ashes were subjected to thermal treatment under an inert atmosphere in a rotary kiln and in sealed ampoules at 400 °C. The concentrations, degrees of chlorination and congener profiles of the POP in the treated ashes and emitted gases were compared to those for the untreated ashes. The trends observed for PCDF mirrored those for PCN, while the trends for PCDD closely resembled those for PCB. The PCDF congener profiles of the kiln ash were similar regardless of the initial ash composition, suggesting that the mechanisms of PCDF formation were similar in all cases. The fourth paper describes the surface characterization of the three fly ashes studied in paper three by SEM, EDX, XPS and XRD. In addition, the thermal desorption and subsequent degradation of POP from the ashes was studied at temperatures of 300-900 °C. The composition of the gases released as the temperature increased differed between the ashes and depended on their composition. Doping experiments using isotopically labelled PCDF and PCDD suggests that PCDD desorbed at lower temperatures than PCDF. This thesis examines several problems relating to POP formation during MSW incineration, from sampling to the ultimate fate of incineration residues. The results obtained illustrate the wide range of processes that contribute to thermal POP formation and degradation during and after MSW incineration. / Förbränning av hushållssopor är en vanlig metod för att hantera ett växande avfallsproblem. Metoden har flera fördelar, såsom minskning av volym och vikt, sterilisering och energiåtervinning. Sopförbränning har dock vissa nackdelar och det mest debatterade är sannolikt utsläpp av persistenta organiska föroreningar (POPs) som polyklorerad dibensofuran (PCDF), dibenso-p-dioxin (PCDD), bifenyl (PCB) och naftalen (PCN). Det finns totalt 210 PCDF- och PCDD- kongener, med mellan ett till åtta klor på kolskelettet, varav 17 är giftiga med hormonstörande och cancerframkallande egenskaper. Även tolv av totalt 209 PCB-kongener samt minst två av totalt 75 PCN-kongener uppvisar liknande egenskaper. Dessa klorerade organiska föroreningar bildas då rökgaserna kyls ner i sopförbränningsanläggningarna och avlägsnas från rökgaserna med hjälp av filter och hamnar i flygaskan. Denna avhandling handlar om bildning och nedbrytning av POPs i sopförbränningsrelaterade processer.   Den första artikeln är en fallstudie där PCDD bildas i filtren i en fullskalig sopförbränningsanläggning. Bildningen ledde till förhöjda halter organiska föroreningar i rökgaserna, vilket ledde till ökade utsläpp. Den funna bildningsvägen för PCDD i filtren befanns sannolikt bero på kondensation av klorfenoler på filterytorna. Den andra artikeln är en valideringsstudie av en kylprob avsedd att användas vid rökgasprovtagning vid hög temperatur (&gt; 450 °C) för att undvika bildning av POPs under provtagningen. Studien bekräftade att majoriteten av PCDF- och PCDD- bildning i rökgaser från sopförbränning sker vid temperaturer under 600 °C. I den tredje artikeln berättas om behandling av tre olika flygaskor från olika sopförbränningsanläggningar. Askorna behandlades vid 400 °C i inert atmosfär i både en roterugn och i förseglade ampuller. De resulterande koncentrationerna, kloreringsgraderna och kongenprofilerna av de organiska föroreningarna jämfördes. Likheter hittades mellan PCDF och PCN, medan PCDD och PCB betedde sig på ett annat sätt. Studien fann också att PCDF kongenprofiler i aska som behandlats i roterugnen liknade varandra, oberoende av askornas sammansättning, vilket tyder på en liknande bildningsväg. För den fjärde artikeln, genomfördes ytkarakterisering (SEM, EDX, XPS och XRD) på de tre flygaskorna från artikel tre som sedan hettades upp från 30 °C till 900 °C i vacuum. Det som frigjordes på grund av uppvärmningen samt nedbrytningsprodukter från askorna studerades med hjälp av masspektrometri och infraröd spektroskopi. Studien fann att de gaser som frigjordes när temperaturen ökade skilde mellan askorna, beroende på deras sammansättning. Studien fann också att när aska dopad med isotopmärkt PCDF och PCDD utsattes för samma behandling, frigjordes PCDD vid lägre temperatur än PCDF. Denna avhandling berör flera aspekter av problematiken kring klorerade organiska föroreningar som bildas vid sopförbränning, från provtagning till hur man ska hantera flygaskan. Avhandlingen belyser även olika typer av bildning och nedbrytning av POPs i varma processer kopplade till sopförbränning.

<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.</p>