Humans are exposed to persistent organic pollutants (POPs) such as brominated flame retardants (BFRs, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD)) and perfluoroalkyl acids (PFAAs, specifically perfluoroalkane sulfonate (PFOS) and perfluorooctanoic acid (PFOA)). They are used in consumer products found in cars, offices, homes and day care centers. Diet was earlier thought to be a major human exposure route for legacy POPs, but does not account for body burdens found for many new POPs and indoor exposure from air and dust has been hypothesized as also important. In this thesis, BFRs in air and dust, and PFAAs in dust from different indoor microenvironments in Sweden were analysed, and the results used to estimate human exposure. BFRs and PFAAs were detected in dust from all microenvironments and PBDEs in all air samples. BFR and PFAA exposure occurs mostly in peoples’ homes with toddlers having higher intakes from dust ingestion than adults. Inhalation and dust ingestion play minor roles compared to diet for humans with median exposures, but in worst case scenarios, dust ingestion may be significant for a small part of the Swedish population. Sampling using home vacuum cleaner bag dust and researcher-collected above floor dust was compared. Correlations were seen for ∑OctaBDE and ∑DecaBDE but not for ∑PentaBDE and HBCD. Higher PBDE concentrations were found in above floor dust but higher HBCD concentrations were found in vacuum cleaner bag dust. BDE-47 concentrations were correlated between vacuum cleaner bag dust and breast milk, indicating exposure through dust ingestion. Similar concentrations of PBDEs were measured in indoor and outgoing air from day care centers, apartment and office buildings. Indoor air explained 54-92% of ∑PentaBDE and 24-86% of BDE-209 total emissions to outdoor air in Sweden, supporting the hypothesis that the indoor environment is polluting ambient air via ventilation systems. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Accepted. Paper 3: Accepted. Paper 4: Manuscript.</p>

Polybrominated diphenyl ethers (PBDEs) are a widely used class of flame retardants that are important sources for contamination in the marine environment. Sediments serve as a large reservoir for PBDEs due to their large sorption capacity. This research assessed the presence and distribution of PBDEs in Hillsborough Bay, a subdivision of Tampa Bay, FL, by determining levels in surface sediment samples, creating a historical profile of the contaminant in a sediment core taken from within the bay, and investigating sediment characteristics that control their distribution. Compositional patterns and temporal distributions of 8 of the 209 congeners of PBDEs (BDE-28, -47, -99, -100, -153, -154, -183 and 209) were determined in sediment surface samples and a sediment core collected throughout the study area. Contaminant concentrations varied spatially due to proximity to sources and the spatial variability of physical processes that suspend or remove contaminants from the water column. Concentrations in the bay also varied in time with factors such as wind, precipitation, and subsequent freshwater runoff. PBDE contamination in surficial sediments from various regions of Tampa Bay is not well correlated with sediment grain size or organic matter content, but these factors may be more important in suspended sediments which may control the fate of these contaminants in the bay. The results from this investigation can be used in understanding the extent of PBDE pollution, identifying sources, as well as implementing management strategies for Hillsborough Bay.

Summary Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants. The addition of these chemicals to electrical and electronic equipment, building materials, carpet and textiles reduces flammability and therefore harm and destruction caused by unwanted fire. These chemicals are now internationally ubiquitous in the environment and humans because of their increased usage and physical and chemical properties of persistence and lipophilicity. Although Australian data on both the concentrations and the sources and exposure pathways was limited, a preliminary study of PBDEs in 10 pools of human blood serum revealed that concentrations of PBDEs in Australia were comparatively higher than most countries with the exception of Canada and the USA. The aim of this project was to determine the concentrations of PBDEs in the Australian population and to examine the possible sources and pathways of exposure in humans. Experimental evaluation of PBDE exposure matrices included samples of: sediment (n=46), air (n=19), dust (n=19), surface wipes (n=10) and human milk (157 samples combined into 17 pools, n=10 individual samples); and the general population using human blood serum (10552 samples combined into 169 pools). With accumulating evidence regarding age differences in PBDE concentrations, the scope of this project was broadened to include a focus on infants and young children. This study found that PBDE contamination was widespread in the Australian environment and human population. In sediment, PBDEs were relatively low at the majority of sites with mean ± standard deviation and median ΣPBDE concentrations across all sites of 4707 ± 12580 and 305 pg g-1 dw, respectively. There were elevated concentrations found downstream of sewerage treatment plants; in areas dominated by industrial and urban land-use types; and in estuarine compared to freshwater environments. PBDEs were detected in air, dust and surface wipes. Concentrations on the whole were found to be higher indoors compared to outdoors and in offices compared to homes. ΣPBDE concentrations ranged from 0.5 -179 pg/m3 for homes and 15 - 487 pg/m3 for offices and at the two outdoor sites the concentrations were 1.7 and 6.8 pg/m3. PBDEs were detected on 9 out of 10 surfaces (e.g. television, refrigerator, DVD player) sampled and ranged from non-detectable to 5985 pg/cm2 while in dust, ΣPBDEs ranged from 87 - 733 ng/g dust in homes and 583 - 3070 ng/g dust in offices. PBDEs were detected in all individual and pooled samples of human milk and blood serum and the ΣPBDE and BDE-47 concentrations ranged from 5.5 to 103 and 0.6 to 55 ng/g lipid, respectively. There were no regional differences in concentrations in human milk or blood serum and in general PBDE concentrations were higher in males than in females. Although no temporal trend was apparent in samples of human milk or blood serum collected between 2002 and 2008, the ban on penta- and octa-BDE commercial products in several countries has only been in place since 2004. Hence, effects of the ban may not be reflected in human body burden for several years. The concentrations of PBDEs were found to be highest in young children aged 2 – 5 years of age where concentrations were up to 10 times greater than those detected in adults. Congener profiles for sediment, air, dust and surface wipes were mostly dominated by BDE-209. In human milk and serum, BDE-47 was dominant while BDE-209 contributed only 3% in human milk and was not determined in serum. Concentrations of PBDEs found in Australian human and environmental samples were lower than those reported from North America but higher than those reported from Europe and Asia. The results of modeling and the assessment of matched samples of human milk, indoor air and dust showed that body burden could be partly explained by exposure via food, air, dust and human milk as well as clearance (half-life) data. However, the higher than expected concentrations in young children indicated that there are likely to be missing sources and exposure pathways and/ or the clearance data is inaccurate. The results of this thesis provide baseline data on PBDE concentrations in Australia and will prove important for long term monitoring of the effect of changes in usage rates of these chemicals. It is important to understand the specific sources and exposure pathways of PBDEs in infants and young children in order to identify intervention methods whereby exposure to this vulnerable population can be reduced. In terms of the future use of PBDEs or other flame retardant chemicals, it is important that the risk-benefit ratio is regulated so that the minimization of human exposure and potential associated negative health effects is balanced with the reduction of harm caused by fire.

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.

The diploma thesis is focused on the issue of the presence of POPs in the surface water and sediments. Monitored compounds were chosen from the group of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDE). Samples were collected in selected localities in the Slovak and the Czech Republic. Selected analytes were extracted with hexane from the aqueous matrix. Analytes were isolated by the ultrasonic extraction using a solvent mixture of hexane-dichlormethane from the solid matrix and the resulting extract was cleaned up by the column chromatography filled with the florisil and the silica gel. Target compounds were analysed by GC/ECD finally. Obtained results show the level of contamination in selected localities in the Slovak and the Czech Republic.

La DCE a pour principale ambition d’harmoniser les politiques de l’eau sur un plan européen et d’atteindre le bon état des eaux d’ici 2015. L’évaluation de ce “bon état” implique en outre de dresser l’inventaire, dans les masses d’eau, des 33 substances prioritaires listées en annexe X de la DCE (annexe X, décision No 2455/2001/EC) et pour lesquelles des normes de qualité environnementales (NQE) ont été fixées (Directive 2013/39/EU). Parmi ces substances figurent les polychloroalcanes (SCCPs) et les polybromodiphényléthers (PBDEs) appartenant à la catégorie des micropolluants halogénés “émergents”. D’un point de vue analytique, leur détermination dans l’eau constitue actuellement un enjeu majeur, tant sur le plan de l’échantillonnage que de la sensibilité.Dans ce contexte, ce travail de thèse s’est attaché au développement d’une méthode d’analyse des SCCPs dans les eaux par SPME couplée à la GC/ECNI-MS. Les limites de quantification inférieures à 0,2 µg.L-1 et son degré d’automatisation font de cette méthode un outil de choix pour assurer le monitoring des milieux aquatiques tels que requis par la DCE. En complément de l’approche classique, un pilote de calibration en laboratoire pour l’étalonnage d’échantillonneurs passifs a pu être mis en place et validé pour la calibration des MESCO avec les HAPs. La participation à un essai interlaboratoire a permis de tester l’applicabilité des MESCO et des SR pour l’analyse des PBDEs en sortie de station d’épuration. Enfin la mise en application des LDPE, SR et MESCO sur l’étang de Berre a permis d’obtenir des résultats encourageants quant à l’applicabilité de ces échantillonneurs passifs pour l’analyse des SCCPs et PBDEs. / In order to achieve good water quality for 2015, the water framework directives (WFD 2000/60/EC and 2013/39/EU) force European countries to monitor the quality of their aquatic environment. For this purpose, all water bodies shall be monitored for all the 33 priority substances listed in annex X of WFD (annex X, decision No 2455/2001/EC) and for which environmental quality standards (EQS) were fixed (Directive 2013/39 / EU). Among these substances, we found the short chain chlorinated paraffins (SCCPs) and the polybrominated diphenyl ethers (PBDEs) belonging to the class of emergent halogenated micro-pollutants. From an analytical point of view, the analysis of SCCPs and PBDEs in water is still a major challenge, either in terms of sampling or sensitivity.In respect of WFD, this thesis work has, among other things, aimed to develop a method to analyze SCCPs in water by using SPME coupled with GC/ECNI-MS. The limit of quantification below 0.2 µg.L-1 and its degree of automation makes this method a tool of choice to ensure the monitoring of the aquatic environment as required by the WFD. In addition to the traditional approach, a laboratory system for passive sampler calibration was also developed and validated to calibrate MESCO for PAHs analysis. Moreover, our participation in an inter-laboratory study, has served to test the applicability of MESCO and SR for the analysis of PBDEs in a waste water treatment plant. Finally the deployment of LDPE, SR and MESCO in Berre lagoon has yielded some encouraging results about applicability of these passive samplers to analyze SCCPs and PBDE in water.

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>

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in a number of common household and commercial products around the world. PBDEs enter the environment in a variety of ways, such as through emissions, leaching from end-of-life electronics in landfills, and incineration. While many countries have phased out the manufacturing of penta-, octa-, and deca-PBDEs or have banned the manufacture and use of these congeners altogether, these persistent organic pollutants (POPs) continue to be detected in humans and the environment. This study investigates spatial and temporal variations of selected PBDEs in the air of the Nandamojo watershed area in Costa Rica by comparing air concentrations of PBDEs in the dry winter vs. wet summer seasons and rural vs. urban areas and also investigates the impact of anthropogenic activities on air concentration of PBDEs. This study is significant to the field, because there are no baseline studies nor are there currently any monitoring programs to assess the environmental levels of PBDEs or other POPs for this region of the Guanacaste province. Baseline information is needed to track spatial and temporal trends as well as evaluate the effectiveness of control measures employed nationally and internationally. Samples obtained from passive air sampling devices were analyzed via GC/MS for a number of congeners. PBDE-47 and -99 were found to be the congeners present in greatest concentration in air samples from the Nandamojo watershed area. Air concentrations were estimated assuming an average sampler uptake rate of 3.5 m3/day and ranged as follows: ΣPBDE5 35.20-1549.25 pg/m3 over the entire study. The presence of PBDEs in remote and pristine environments indicates that PBDEs are now a global concern. This study suggests that the spatial and temporal distribution patterns observed are strongly related to anthropogenic activities and presence of a population similar to that observed in other studies. The presence of PBDEs has become a global issue and, as such, these results provide background information on air concentrations of PBDEs for use in a global-scale multimedia model. In order to monitor PBDEs globally, it is imperative to implement and/or expand surveillance programs internationally.

Decabromodiphenylether (deca-BDE) and triclosan (2,4,4'-trichloro-2'-hydroxydiphenylether) are used in consumer products as flame retardant and bactericide, respectively. Dermal contact is a major human exposure pathway. Deca-BDE and triclosan are known to be photolytically degraded to compounds like lower-BDEs and dioxins. My hypothesis is that photolysis of deca-BDE and triclosan generates free radicals and degradation products which cause toxic effects including cytotoxicity, growth inhibition, oxidative stress and genotoxicity in skin. To test this hypothesis radical formation and photolytic products of deca-BDE and toxic effects of deca-BDE and triclosan alone/with UV-exposure were determined using immortal human keratinocytes (HaCaT) and primary human skin fibroblasts (HSF). My electron paramagnetic resonance and GC-MS studies indicate that deca-BDE is photoreactive and UV irradiation of deca-BDE in organic solvents generates free radicals and lower-BDEs. The free radical formation is wavelength-dependent and positively related to the irradiation time and deca-BDE concentration. In structure-activity relationship studies with deca-BDE, octa-BDE, PBB 209, PCB 209 and diphenyl ether, the presence of halogen atoms (Br > Cl), and/or an ether bond enhance free radical formation. Debromination and hydrogen abstraction from the solvents are the mechanism of radical formation with deca-BDE, which raises concerns about possible toxic effects in UV-exposed skin. In cell culture experiments high levels of triclosan plus UV irradiation and repetitive deca-BDE and UV exposures caused synergistic cytotoxicity in HaCaT. However, neither triclosan nor deca-BDE can be regarded as a phototoxicant following the OECD test and evaluation guidelines. In HSF, no synergistic cytotoxicity was observed, although HSF were more sensitive to deca-BDE and triclosan alone than HaCaT. Contrary to expectations, the photodegradation products of triclosan were less toxic than triclosan itself to HaCaT. However, UV irradiation of triclosan-exposed cells produced a dose dependent increase in intracellular oxidative stress (dichlorofluorescein formation). Comet experiments did not show consistent results of genotoxicity in HaCaT. Overall, deca-BDE and triclosan had no or weak phototoxic potential in cells with the experimental conditions employed. To my knowledge, my research is the first prove of free radical formation during UV irradiation of deca-BDE and the first investigation of phototoxicity of deca-BDE and triclosan in human skin cells.

Presented is a study of persistent organic pollutants in Australian sewage sludge, focusing on environmental monitoring and a sewage sludge land application human health risk contaminated with these compounds. The chemicals of concern were: • Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and