This study is to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs) in the sediments of the coastal areas along the southwestern Taiwan. Sediment samples were collected and analyzed to investigate the possible sources and characteristics. The concentration of PAHs and PBDEs ranged from 15 to 907 and from N.D. to 92 ng/g dry wt, respectively, and congener compositions for PBDEs were dominated by BDE-209 (68.8-77.9%). Total PAH concentrations we found in coastal sediments were lower than those of other studies in the world. The highest £UPAH values were observed at Kaohsiung coastal areas, while the lowest £UPAH values were found at Tainan coastal areas. Total PBDE concentrations in coastal sediments were lower than those in river sediments. Sources of PBDEs in those sediments from coastal areas were different from those of river sediments because compound compositions in both areas were different. Both total PAH and total PBDE concentrations were significantly correlated with total organic carbon (TOC) and mean particle size (r=0.51, -0.42, p<0.01; r=0.80, -0.85, p<0.01). In comparison with sediment quality guidelines (SQGs), the PAH concentrations of all sediment samples were lower than those outlined in the criteria, that suggests no evident adverse biological effects caused by PAHs. According to the results of hierarchical cluster analysis (HCA) and principal component analysis (PCA), the stations can be clustered into three groups. In general, PAHs in sediments of Kaohsiung coastal area were mainly contributed from combustion sources, while those in Kao-ping estuary were mainly from petrogenic sources. However, both sediments in Tainan and Hsinda harbor coastal areas were mainly contributed from biogenic sources.

Os éteres de difenilas polibromados (PBDEs) são largamente usados como retardantes de chama e têm sido detectados em diversas amostras biológicas, devido às suas características físico-químicas e bioacumuladoras, as quais fazem com que estes compostos tenham uma elevada persistência no meio ambiente. A exposição a estes compostos pode ser nociva ao homem e aos organismos vivos, uma vez que muitos estudos têm relatado que este composto possui atividade citotóxica. Desta forma, no presente estudo, investigamos o mecanismo de ação dos BDE-47, BDE-99, BDE-154 e BDE-209 sobre o processo autofágico de células HepG2, pois além de ser um processo de reciclagem de moléculas intracelular, a autofagia atua ainda na citoproteção celular. Foram realizados ensaios de imunocitoquímica para detecção de alterações no processo autofágico, no qual foi avaliado, sob microscopia de fluorescência, o padrão de distribuição das proteínas LC3-I e LC3-II; paralelamente, foi realizada a técnica de western blotting para a quantificação de três proteínas associadas ao processo de autofagia - LC3, Beclin-1 e p62. Em nossas análises de imunocitoquímica pode-se observar que os quatro PBDEs em estudo foram capazes desencadear o processo de autofagia, sendo que a magnitude do efeito tóxico foi dependente do tempo de exposição (24 e 48 horas), da concentração utilizada (0,1; 1; 5; 25 ?mol/L) e variável de acordo com o congênere em questão, sendo os BDE-47 e BDE-99 os que apresentaram maior potencial de ativação da autofagia. Além disso, esta indução de autofagia ainda pode ser detectada nos ensaios de western blotting, pois os PBDEs alteraram os níveis de LC3-II, Beclin-1 e p62, havendo um padrão de toxicidade semelhante ao visualizado nos ensaios de imunoistoquímica. Adicionalmente, devido ao fato dos PBDEs poderem se acumular no meio ambiente, principalmente em organismos aquáticos, uma análise dos efeitos destes compostos sobre um modelo ecotoxicológico foi realizada. O zebrafish (D. rerio) foi utilizado como organismoteste, a fim de avaliar a toxicidade destes contaminantes ambientais sobre seus estágios embrionários e larvais. Foram analisados endpoints de letalidade, subletalidade e teratogenicidade após a exposição aos PBDEs em estudo. Sendo que os compostos BDE-47, BDE-99 e BDE-209 (na presença de luz) apresentaram alterações em pelo menos um dos indicadores avaliados, sendo que o parâmetro mais afetado foi a inflação das bexigas natatórias, indicando uma possível teratogenicidade causada por estes compostos. Por outro lado, os BDE-154 e BDE- 209 (na ausência de luz) não causaram malformações no organismo-teste. Diante dos resultados obtidos, pode-se concluir que estes compostos podem causar alterações na homeostase celular desencadeando o processo autofágico, sendo que se absorvidos por organismos, podem afetar o desenvolvimento de espécies como o zebrafish. / Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and they have been detected in several biological samples due to their physicochemical and bioaccumulating characteristics, which make these compounds to have a high persistence in the environment. The exposure to these compounds can be harmful to man and other living organisms, since many studies have reported that this compound has cytotoxic activity. Thus, in the present study, we investigated the mechanism of action of the BDE-47, the BDE-99, the BDE-154 and the BDE-209 on the autophagic process of HepG2 cells, because beyond being an intracellular molecule recycling process, autophagy acts also in the cell cytoprotection. Immunocytochemistry assays were performed to detect changes in the autophagic process, in which the distribution pattern of the LC3-I and LC3-II proteins was evaluated under fluorescence microscopy. In parallel, the western blotting technique was used to quantify three proteins associated with the autophagy process - LC3, Beclin and p62. In our analyzes of immunocytochemistry it can be observed that the four PBDEs in the study were able to trigger the autophagy process, and the magnitude of the toxic effect was dependent on the exposure time (24 and 48 hours), on the used concentration (0.1; 1; 5; 25 ?mol/L), and it varies according to the congener. The BDE-47 and BDE-99 are the ones with the highest potential for autophagy activation. In addition, this autophagy induction can still be detected in the western blotting assays, because the PBDEs altered the levels of LC3-II, Beclin-1 and p62, with a similar pattern of toxicity as seen in the immunohistochemical assays. In addition, due to the fact that PBDEs may accumulate in the environment, mainly in aquatic organisms, an analysis of the effects of these compounds on an ecotoxicological model was performed. The Zebrafish (D. rerio) was used as a test organism in order to evaluate the toxicity of these environmental contaminants on their embryonic and larval stages. In this study, lethality, sublethality and teratogenicity endpoints were analyzed after exposure to the PBDEs. The BDE-47, BDE-99 and BDE-209 compounds (in the presence of light) presented alterations in at least one of the indicators evaluated, and the most affected parameter was the swim bladder inflation, indicating a possible teratogenicity caused by these compounds. On the other hand, the BDE-154 and the BDE-209 (in the absence of light) did not cause malformations in the test organism. Considering the results, it can be concluded that these compounds are able to cause changes in cellular homeostasis triggering the autophagic process, and whether absorbed by organisms, they can affect the development of species such as zebrafish.

The diversity of choices we have to make everyday influence our environment and ourselves in more ways than most of us realise. Anthropogenic substances, such as flame retardants, date back as early as 450 BC when the Egyptians used alum to reduce flammability. The increasing demand for new articles has led to an increased production of chemical substances, for which many are commercially produced without complete knowledge on properties such as persistence, bioaccumulation and toxicology (PBT). Commercial compounds may be properly tested and denominated as “safe” regarding PBT properties, but their degradation products and/or metabolites may cause environmental impact. The availability of uniform and accurate data for prediction of persistence is of key importance for the understanding of chemical fate. A method to determine the susceptibility of chemicals to undergo oxidation in water has been developed and applied on several organohalogens, including PBDEs and OH-PBDEs. The method was used to determine reaction rates and the group of OH-PBDEs were subsequently subjected to photolysis by use of UV-light. Hence, susceptibility to undergo both oxidation and photolysis for the OH-PBDEs were investigated and compared to previously reported degradation rates on PBDEs. As a final step in promoting the prediction of persistence, Quantitative structure-property relationship (QSPR) models were performed on a set of compounds which had undergone photolytic degradation under similar conditions. The QSPRs were used as a preliminary step in predicting photolysis half-lives for chemical substances and to determine which physicochemical descriptors are of greatest importance thereof. This thesis presents the possibility of performing and assessing oxidation transformations on compounds of low and high water solubility, photolysis transformations in various media and using obtained data to predict behaviour via QSPR models, to promote predictions of persistence.

Persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) and polybrominated diphenylethers (PBDEs), are widely distributed in the environment. Several studies have demonstrated that these pollutants will cause potential impacts such as carcinogenic and mutagenic for human health. In this study, four different types of sampling stations were chosen. Two of the sampling sites are located in Kaohsiung city, which is an industrialized city with densely population in southern Taiwan (KHU and KHC). The other sampling sites are in a rural coastal area (KT) and an offshore island (LY), respectively. We determined the concentrations of PCBs and PBDEs in the atmosphere to identify the spatial and temporal distributions of PCBs and PBDEs in southern Taiwan. Hierarchical cluster analysis (HCA) and principal components analysis (PCA) of congener-specific composition of PCBs and PBDEs were performed with the commercial products to investigate the relationship of regional signatures and possible pollution sources. Finally, back trajectory analysis was undertaken to gain a better understanding of long-distance transport contribution to the studied area. The concentrations of £UPCBs in the ambient air ranged from 9.51 to 482 pg m-3, with an average concentration of 162¡Ó155 pg m-3. The mean PCB concentrations in gas and particle phase were 159¡Ó153 pg m-3 and 3.04¡Ó2.38 pg m-3, respectively. The concentrations of £UPBDEs in the ambient air ranged from 3.42 to 166 pg m-3, with an average concentration of 31.7¡Ó37.3 pg m-3. The average PBDE concentrations in gas and particle phase were 7.22¡Ó6.50 pg m-3 and 23.7¡Ó33.4 pg m-3, respectively. Comparison of the total PCB and PBDE concentrations from the four sampling sites showed that the total PCB and PBDE concentrations at the Kaohsiung urban site (KHU) and Kaohsiung coastal site (KHC) were higher than those at a rural coastal site (Kenting, KT) and an offshore island site (Lanyu, LY), suggesting that densely population and heavy industrial park may be the major contributor of PCBs and PBDEs . Results from HCA, PCA and compositional patterns of PCBs indicate that offshore island site (Lanyu, LY) was different from KHU, KHC and KT. Lower chlorinated congeners (dichlorobiphenyls to hexachlorobiphenyls) were predominant in the gas phase. Since most of the lower molecular weight congeners were below the detection limit, the total PCB concentrations were found at much lower level in LY sampling sites. In addition, a significantly higher proportion of high-chlorinated congeners, was observed at LY, suggesting that there may be local pollution sources in this area. Results from HCA, PCA and compositional patterns of PBDEs indicate that the samples from February and October were dominated by BDE-209, while the samples from July were dominated by BDE-71, BDE-47 and BDE-99, suggesting that this might be due to the significantly low concentrations of suspended particles (PM10) in July. Since much higher temperature was observed in July, these lower brominated congeners may be released much easier from the sediment, water, and brominated-containing products due to smaller molecular size and higher vapor pressure. Moreover, debromination of the deca-BDEs had been observed in the environment. Several studies have shown that photolytic debromination of BDE-209 is possible pathway for the formation of lower brominated-BDEs. TEQ was used to determine the level of pollution for environment and human health. In this study area, the TEQ ranged from 0.145 to 0.878 pg-TEQ m-3, with an average TEQ of 0.0004¡Ó0.0003 pg-TEQ m-3 in gas-phase of ambient air. PCB114 was observed to be the predominant congener in this study.

The current knowledge concerning effects of polybrominated diphenyl ether (PBDEs) on benthic aquatic organisms is still very limited although they have been widely used as fire retardant additives for 3 decades. This study was conducted to evaluate the toxic effects of BDE-47 and BDE-183, the two common congeners of PBDEs in river sediments, on a benthic oligochaete worms, Monopylephorus limosus. The worms were exposed to BDE-47 or to BDE-183 for two or eight weeks. The survival rates of M. limosus decreased significantly when exposed to 700 ng/g dry soil of BDE-47 or BDE-183 for 8 weeks, but not in groups of 1-1000 ng/g BDE-47 for 2 weeks. A total of forty proteins of M. limosus has been expressed and determined by the two-dimensional gel electrophoresis (2-DE). Through the cluster analysis, it was found that the protein expression in the group of 100 ng/g BDE-47 was similar to 10 ng/g BDE-183. The results indicate that the toxicity of BDE-183 was greater than BDE-47 to M.limosus. Although the survival rate of M. limosus was not significantly affected when exposed to BDE-47 or BDE-183 at concentrations of 1 to 100 ng/g, significant differences in protein expression were found. Thus, the analysis of protein expression is more sensitive to detect the toxicological change in M. limosus than the survival test.

The indoor environment is a potentially dominant source of exposure for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). This thesis describes a study on levels, sources, emissions, and fate of PBDEs and PCBs indoors. PBDEs and PCBs air levels in 20 indoor environments in Toronto were sampled and measured. The geometric means of PBDE (Σ10BDE) and PCB (Σ35PCB) concentrations were 0.072 and 7.2 ng m-3 respectively. Statistical analysis on chemical profiles distinguished the chemical sources in the 20 environments. A multimedia indoor environmental model was applied on two test rooms. Estimated PBDE and PCB emission rates were 5.4-550 ng h-1 and 280-5870 ng h-1 respectively. Particle movement dominates within-room transport processes, and dust removal and air advection are the main chemical loss processes. Temperature, particle concentration and deposition velocity, and air exchange rate are the most influential parameters, which can alter source or sink behaviors of household products for the chemicals.

The indoor environment is a potentially dominant source of exposure for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). This thesis describes a study on levels, sources, emissions, and fate of PBDEs and PCBs indoors. PBDEs and PCBs air levels in 20 indoor environments in Toronto were sampled and measured. The geometric means of PBDE (Σ10BDE) and PCB (Σ35PCB) concentrations were 0.072 and 7.2 ng m-3 respectively. Statistical analysis on chemical profiles distinguished the chemical sources in the 20 environments. A multimedia indoor environmental model was applied on two test rooms. Estimated PBDE and PCB emission rates were 5.4-550 ng h-1 and 280-5870 ng h-1 respectively. Particle movement dominates within-room transport processes, and dust removal and air advection are the main chemical loss processes. Temperature, particle concentration and deposition velocity, and air exchange rate are the most influential parameters, which can alter source or sink behaviors of household products for the chemicals.

Polybrominated Diphenyl Ethers (PBDEs) are flame retardants widely used within the United States in various products such as plastics, electronics, textiles and furniture. With an increase in production and usage, PBDEs have recently emerged as a contaminant of concern. Due to their chemical structure, PBDEs have the propensity to bioaccumulate in mammals. In fact, elevated PBDE concentrations have been recorded in human breast milk. Due to the potential widespread exposure to PBDEs, this study investigates human blood concentrations of PBDEs generated through the 2003-2004 National Health and Nutrition Examination Survey. Through the use of statistical modeling, a comparison of mean PBDE concentrations in ng/g lipid is conducted based on age, gender and ethnicity. From a sample of 2337 individuals, the average blood concentration of PBDEs was approximately 81 ng/g lipid. The average PBDE concentration of males was significantly higher than females, using a 95% confidence level. In addition, PBDEs detected in human blood ranged approximately from 0.05 to 3676 ng/g lipid, with the highest concentrations found in black males. Also, a logistic regression analysis is conducted to determine whether an increase in background PBDE concentrations is a risk factor for obesity. Furthermore, the analyses of PBDEs are repeated for phthalates and polychlorinated Biphenyls for comparison. Finally, the measured concentrations of PBDEs are also compared to health outcome data known to show potential risk.

The present studies determine the accumulation of persistent organic pollutants (POPs) in three pinniped species, evaluate the relationship with relevant biomarkers of exposure, and calculate toxic effect thresholds. Stranded harp and hooded seals were found to be accumulating PBDEs at levels which could pose a based on threshold levels determined in this study. Northern fur seals are accumulating all three classes of POPs (PCBs, PBDEs, and OCPs) with significant relationships being seen with blubber percent lipid. Correlations between contaminant concentrations and expression levels of relevant biomarkers were seen potentially indicating an effect on multiple pathways. Overall risk can be hard to determine due to factors such as sex and age. Broad threshold response values and hazard quotients were calculated for toxic effect endpoints in pinnipeds. Overall these results suggest that certain populations of pinnipeds are at high risk of experiencing toxic effects due to POP exposure, but it is important to understand effects even at lower concentrations. The relationship between exposure, toxic effects, and other stressors, both environmental and physiological, can impact the overall fitness and survival of pinnipeds.

Existem muitos estudos sobre a ocorrência de poluentes orgânicos persistentes (POPs) no ambiente marinho utilizando bioindicadores como os tubarões. Entretanto, no Brasil, ainda há carência de dados de POPs nesses organismos. O objetivo desta pesquisa foi investigar a ocorrência e o comportamento dos PCBs, pesticidas organoclorados e PBDEs no ambiente marinho, a partir da utilização dos tubarões como indicadores. Musculatura e fígado de vinte tubarões-azul (Prionace glauca) foram coletados em agostosetembro de 2008. Os PCBs foram os poluentes predominantes, presentes em 80% das amostras, com concentrações variando de <n.d. a 427,28 ng.g-1 de peso úmido. Os diclorodifeniletanos apresentaram concentrações variando de 0,43 a 202,42 ng.g-1 de peso úmido, no qual o 4,4´-DDE foi o composto mais significativo, com 77,6% de contribuição para os DDTs totais. As concentrações no fígado foram 1-2 ordens de grandeza mais elevadas, em relação às de musculatura. Houve um padrão de distribuição dos poluentes com níveis equivalentes entre indivíduos imaturos. Os machos maduros apresentaram concentrações de POPs sensivelmente maiores que as fêmeas maduras, indicando a transferência dos POPs para os filhotes. Os resultados demonstraram a ampla distribuição desses poluentes no ambiente marinho. / There are many studies about the occurrence of persistent organic pollutants (POPs) in the marine environment using sharks as bioindicators. However, there is still a lack of data of POPs in those organisms in Brazil. The goal of this research was to investigate the occurrence and behavior of PCBs, organochlorine pesticides and PBDEs in the marine environment, using sharks as indicators. Muscle and liver of twenty blue-sharks (Prionace glauca) were collected in august-september 2008. The PCBs were the predominant pollutants and being present in 80% of samples, with concentrations ranging from <n.d. to 427.28 ng.g-1 wet weight. The dichlorodiphenylethanes present concentrations ranging from 0.43 to 202.42 ng.g-1 wet weight, where the 4,4´-DDE was the most significative compound, with contributions of 77,6% of the total DDTs. The concentrations in the liver were 1-2 orders of magnitude higher than in the muscle. There was a distribution pattern of the pollutants, with equivalent levels among the immature specimens. The concentration of POP was significantly higher in the mature males and relatively lower in the mature female, showing the maternal transference of POPs to the pups. The results have demonstrated a wide distribution of these pollutants in the marine environment.