Polychlorinated biphenyls (PCBs) are widespread persistent organic pollutants. The metabolism of PCBs by various organisms involves many steps that can lead to the formation of a wide range of metabolites. These metabolites frequently exhibit a toxicity and biodegradability different than the parent compounds. There is currently little information available about the biological effects of PCB hydroxylated metabolites that can be generated by various organisms and potentially released into the environment. The objective of the present research is to compare the toxicity of selected PCB congeners and their corresponding mono-hydroxylated metabolites. To achieve this objective, the following specific aims were performed: (1) to determine the effect of selected PCBs and PCB hydroxylated metabolites on the growth rate of a model PCB-degrading bacterium, Burkholderia xenovorans LB 400, (2) to determine the microbial toxicity of PCBs and PCB metabolites using the bioluminescent assay Microtox®, and (3) to determine the estrogenicity of PCBs and PCB metabolites using the Yeast Estrogen Screen assay (YES). The effects of a range of PCBs (PCB-2, -3, -8, -9, -30, -35, -36, -39, -61, -68, and -79) and their mono-hydroxylated metabolites on the growth rate of the PCB degrader, Burkholderia xenovorans LB400, were recorded. The results showed that the parent PCBs (50 mg L-1) did not affect the growth rate of LB400 although their hydroxylated metabolites strongly inhibited microbial growth. Using Microtox® assay, Parent PCBs (50 mg L-1) did not exhibit observable toxicity, while their hydroxylated metabolites showed a high level of toxicity (EC50 ranges from 2 mg L-1 to 46 mg L-1). Results using the YES assay also showed that the estrogenicity of hydroxylated metabolites of PCBs (50 mg L-1) was higher than the parent PCBs. The results obtained from the present study show that mono-hydroxylated metabolites of PCBs are more toxic than the corresponding parent PCBs. Because hydroxylated PCB derivatives are produced by a range of organisms and potentially released into the environment, this work raises new concerns associated with the environmental fate of PCBs. / Civil Engineering

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PCBs are synthetic organic compounds known for their toxicity to many organisms and are notorious for having large discrepancies between measured and nominal concentrations. Historically thought to be less toxic, non-dioxin-like (NDL) PCBs represent the majority of congeners and are capable of eliciting neurotoxic effects. NDL-PCBs remain understudied, including their effects on aquatic organisms. In the first study, I collected extensive chemistry data and data on neurobehavioral and cardiac endpoints to test the acute effects of exposure to an NDL-PCB mixture on early life stage zebrafish. Neurobehavioral effects observed in the first study indicated a potential for longer term behavioral effects in these fish. In the second study, I collected data on feeding, social, and memory behavior of zebrafish at time points beyond the acute exposure from the first study. Acute and longer-term behavioral endpoints in the first and second studies demonstrated effects from PCB exposure but did not indicate mechanisms. In the third study, I collected untargeted and targeted metabolomic data on amino acid, sugar, anionic compound, and neurotransmitter profiles to determine the specific pathways affected by exposure to an NDL-PCB mixture. These combined data from these studies provide a unique insight into the chemical profile of an NDL-PCB mixture in biological applications and synthesize acute, longer-term, and mechanistic effects on developing zebrafish. These data fully illustrate an adverse outcome pathway from toxicokinetic to population level effects.

PCBs are among the most problematic marine contaminants. Converging towards the oceans via the rivers and the atmosphere, they concentrate in sediments where they become a permanent threat to organisms living at their contact. PCBs are extremely resistant, bioaccumulated and some congeners are considered as highly toxic. The North Sea is considered as a highly contaminated area ;however little information is available regarding the impact of PCBs on key benthic organisms of this region.<p>Ubiquist, abundant and generally recognized as a good bioindicator species, the common NE Atlantic sea star Asterias rubens (L.) is an ecosystem-structuring species in the North Sea and was chosen as an experimental model. The present study focused on the characterization of PCB bioaccumulation in A. rubens exposed through different routes (seawater, food, sediments) and on subsequent biological responses, at immune and sucellular levels. The considered responses were respectively (i) the production of reactive oxyggen species (ROS) by sea stars amoebocytes, which constitutes the main line of defence of echinoderms against pathogenic challenges and (ii) the induction of a cytochrome P450 immunopositive protein (CYP1A IPP) which, in vertebrates, is involved in PCB detoxification.<p>Experimental exposures carried out have shown that A. rubens efficiently accumulates PCBs. Exposure concentrations were always adjusted to match those encountered in the field. PCB concentrations reached in sea stars during the experiments matched the values reported in field studies ;therefore our experimental protocol was found to accurately simulate actual field situations. Uptake kinetics were related to the planar conformation of the considered congeners :non-coplanar PCB uptake was described using saturation models, whereas coplanar PCBs (c-PCBs) were bioaccumulated according to bell-shaped kinetics. Non-coplanar congeners generally reached saturation concentrations whithin a few days or a few weeks, which means that sea stars can be used to pinpoint PCB contamination shortly after occurrence. On the other hand, c-PCB concentrations reached a peak followed by a sudden drop, indicating the probable occurrence of c-PCB-targeted metabolization processes in sea stars. Our experimental studies also demonstrated that seawater was by far the most efficient route for PCB uptake in sea stars and that even if PCB levels in seawater are extremely low compared to sediment-associated concentrations, seawater constitutes a non-negligible route for PCB uptake in marine invertebrates. Among the different body compartments, bodywall displayed the highest bioaccumulative potency and can therefore be considered as particularly interesting for field biomonitoring applications. Rectal caeca, which play a central role in digestion and excretion processes in sea stars, have also rised particular interest as results suggest these organs could be involved in the elimination of PCB 77 degradation products. <p>The field work carried out during the present study showed that PCB concentrations measured in A. rubens tissues reflect environmental levels of certain congeners. As it was the case in experimental conditions, A. rubens differentially accumulated PCB congeners according to their planarity. Strong relationships were found between concentrations measured in sediments and those determined in sea stars body wall for certain non-coplanar congeners (e.g. 118 and 138), thus allowing to consider A. rubens as a suitable bioindicator species for medium-chlorinated PCB congeners. On the other hand, sea stars appeared to be able to regulate -to a certain extent- their content in coplanar PCBs. This implies that (i) A. rubens cannot be strictly considered as an indicator organism for c-PCBs and (ii) c-PCBs probably affect essential aspects of sea star biology, potentially leading to deleterious effects.<p>The present study addressed effects of PCB exposure on A. rubens biology, in both experimental and field conditions. In experimental conditions, PCBs were found to significantly alter ROS production by sea stars amoebocytes. This alteration also occurred in a congener-specific way :c-PCBs were found to significantly affect, and probably impair sea stars immune system, whereas non-coplanar congeners had no effect. In the field, the PCB contribution to immunotoxicity could not be determined because none of our studies considered ROS production along with c-PCB concentration measurements. However, the levels of ROS production by sea stars amoebocytes measured in field and experimental conditions were found to potentially lead to altered immunity, and therefore to impair sea stars defence against pathogenic agents. <p>A specially designed ELISA was used to measure CYP1A IPP in experimental and field conditions. Experimental work has shown that the induction of this protein was related to PCB exposure in a congener-specific fashion :c-PCBs alone were found to strongly induce the production of CYP1A IPP according to a dose-dependent relationship. These results have highlighted many similarities between the dioxin-like responsiveness of CYP1A IPP induction in sea stars and that occurring in vertebrates. This strongly suggests similarities in the toxicity-triggering mechanism of dioxins and c-PCBs. In the field, CYP1A IPP induction was found to be significantly related to PCB levels determined in bottom sediments. It can thus be considered as a valuable biomarker. Further research is however needed to better characterize the influence of physico-chemical and physiological parameters on CYP1A induction to refine the interpretation of the information gathered via this biomarker. <p>Results obtained in our study have lead to questionning international regulations applying to PCB biomonitoring in the marine environment. For instance, we strongly suggest that the selection of congeners to be systematically considered should be revised to include c-PCBs. Indeed, in our experiments PCB toxicity was almost always attributable to the sole c-congeners. Historically, determination of c-PCB concentrations was extremely difficult due to analytical limitations ;however, nowadays, these problems have been overcome and do no more justify their exclusion from monitoring studies. <p>Although A. rubens appeared to be quite resistant to PCB contamination, levels measured in sea stars from the southern North Sea can possibly affect their immune and endocrine systems in a subtle way, but with relatively low risk for this species at the short-term. However, this does not mean that other species in this region undergo similarly low risks, or that sea star-structured ecosystems may not become affected in the long-term<p> / Doctorat en sciences, Spécialisation biologie animale / info:eu-repo/semantics/nonPublished

The blood-brain barrier (BBB) is a dynamic interface, mainly consisting of highly specialized brain microvascular endothelial cells (BMECs) that segregate the central nervous system (CNS) from the peripheral circulation. Impairment of the BBB, due to disruption of tight junction (TJ) proteins and inflammatory responses, may initiate and/or contribute to the progress of CNS disorders, including stroke. Stroke is the second leading cause of death worldwide. It has been shown that aging and environmental pollutants can induce brain endothelium dysfunction, and are considered as risk factors for stroke. Deficiency of telomerase is highly linked with aging-associated vascular diseases. Evidence indicates that patients with shorter telomere length are at higher risk of heart disease or stroke. Results in this dissertation address the influence of telomerase reverse transcriptase (TERT), a key component of telomerase, on the BBB integrity in the context of ischemic stroke induced brain injury. Our results indicate that aging-related BBB alterations aggregate the stroke outcomes by inducing oxidative stress and stimulating proinflammatory responses on the brain microvessels. The ability of the BBB to protect the brain from harmful compounds indicates that the BBB may be targeted by chemical toxicants in the peripheral circulation. Polychlorinated biphenyls (PCBs) are persistent organic pollutants that frequently bind to nanoparticles (NPs) in the environment. Our results demonstrate that binding PCB153, one of the most abundant PCB congeners in the environment, to silica nanoparticles (PCB153-NPs) potentiates cerebrovascular toxicity and stroke outcomes via stimulation of inflammatory responses and disruption of BBB integrity. These events are mediated by activation of toll-like receptor 4 (TLR4), which subsequently recruits tumor necrosis factor-associated factor 6 (TRAF6) and initiates the production of multiple inflammatory mediators. Research presented in this dissertation demonstrates that aging and environmental pollutants play crucial roles in modifying the function of the BBB through alterations of inflammatory responses and TJ protein expression, which further contribute to the progression of stroke-induced cerebral ischemic injury.

Bifenilas policloradas (PCBs) foram produzidas comercialmente entre 1929 e meados da década de 1980 para propósitos industriais. As mesmas propriedades que despertaram o interesse industrial, tais como: inércia química, alta constante dielétrica, resistência à queima; foram responsáveis pelo espalhamento dos PCBs em todos os compartimentos ambientais, de tal forma que são encontrados em amostras de tecidos adiposos de animais e humanos, leite, sedimentos dentre outras matrizes. Enormes quantidades de PCBs continuam em uso ou estão estocadas a espera de uma destinação final. No presente estudo demonstramos o uso da reação de hidrodescloração catalítica como forma de destruição/destoxificação de bifenilas policloradas. Para tanto, a reação foi estudada em amostras reais de PCBs (óleo dielétrico - Ascarel®), amostras comerciais (Aroclor® 1242 e 1254) e amostra sintética (2,4-diclorobifenila). O estudo se baseia no uso de solventes orgânicos como meio reacional e paládio suportado em carvão ativado como catalisador, devido à sua seletividade para a reação desejada, bem como sua baixa capacidade de hidrogenar compostos aromáticos. xii A condição experimental ótima para a hidrodescloração foi determinada a partir da aplicação de planejamento experimental do tipo Doehlert. Esta condição ótima foi aplicada com sucesso a PCBs contidos em outras matrizes. A cinética da reação é apresentada para o 2,4-diclorobifenila como estudo de caso e uma proposta de mecanismo da reação de hidrodescloração de PCBs é apresentada baseada nos resultados experimentais. / Polychlorinated biphenyls (PCBs) were produced between 1929 and the 1980s for industrial applications. The same properties that make it a chemical of interest for industrial applications, such as: chemical inertness, high dielectric constant, fire resistance; were responsible for the widespreading of PCBs over all enviornmental compartments. They can be found in samples of fat tissues of humans and animals, milk, sediments, among other matrices. Enormous quantities of PCBs are still in use or stocked waiting for a final destination. In the present study, we have shown the use of catalytic hydrodechlorination as an alternative for the destruction/detoxification of polychlorinated biphenyls. For this, the reaction was studied in real samples of PCBs (dielectric oil - Ascarel®), commercial samples (Aroclor® 1242 e 1254) and pure chlorinated biphenyls (2,4-dichlorobiphenyl). The study is based in the use of organic solvents as reactional media and palladium supported in activated carbon as catalyst, due to its selectivity for the desired reaction and to its low capacity to hydrogenate aromatic compounds. xiv The optimal hydrodechlorination condition was determined through the application of a Doehlert experimental planning. This optimal condition was applied with success to PCBs contained in other matrices. The reaction kinetics for 2,4-dichlorobiphenyl was presented as a case study and a mechanistic proposal was presented for the hydrodechlorination of PCBs based on these experimental conditions.

A reação de hidrodescloração catalítica (HDC) de bifenilas policloradas (PCB) foi estudada em diversos sistemas reacionais: solventes orgânicos, dióxido de carbono supercrítico, presença e natureza de aditivos (bases e co-solventes) a temperaturas na faixa de 25 &#176;C a 100 &#176;C e pressões de 1 bar até 250 bar. Os reagentes utilizados foram um composto modelo (2,4- diclorobifenil), misturas comerciais de PCB (Aroclor, Ascarel) e outros compostos halogenados (clorobenzenos e bromoclorobenzeno). Os catalisadores avaliados, paládio suportado em carvão ativo (Pd/C), paládio suportado em sílica mesoporosa (Pd/SiO2), nanopartículas ferromagnéticas de paládio (FFSiNH2Pd), e nanopartículas ocas de paládio (PdNP) e de platina (PtNP), mostraram-se versáteis nas mais diversas condições, quer sejam condições supercríticas, presença ou não de água, presença e natureza da base e diferentes doadores de hidrogênio. Em dióxido de carbono, dois regimes reacionais foram avaliados: dióxido de carbono subcrítico, onde o gás atua como agente expansor da fase líquida ao se dissolver nela permitindo que a reação ocorra em uma fase líquida rica em gás hidrogênio; e dióxido de carbono supercrítico, sistema onde a temperatura influencia fortemente a reação e a pressão tende a ter efeito negativo sobre a velocidade de reação, devido a efeitos de diluição e de competição das moléculas do gás com as moléculas dos reagentes. A condição reacional ótima foi determinada para o regime supercrítico e dados cinéticos foram obtidos para os regimes sub- e supercrítico. / The catalytic hydrodechlorination reaction (HDC) of polychlorinated biphenyls (PCB) was studied in several reactional systems: organic solvents, supercritical carbon dioxide, presence and nature of additives (bases and co-solvents), in temperatures of 25 &#176;C to 100 &#176;C and pressures of 1 bar to 250 bar. The reagents used were: a model compound, 2,4-dichlorobiphenyl, commercial mixtures of PCB (Aroclor, Ascarel) and other halogenated compounds (chlorobenzenes and bromochlorobenzene). The catalysts evaluated, palladium supported in activated carbon (Pd/C), palladium supported in mesoporous silica (Pd/SiO2), palladium ferromagnetic nanoparticles (FFSiNH2Pd), and hollow palladium ((PdNP) and platinum (PtNP) nanoparticles, showed to be versatile in several conditions, either supercritical conditions, presence or not of water, nature of the base, and different hydrogen donors. In carbon dioxide, two reaction regimes were evaluated: subcritical carbon dioxide, where the gas acts as an expansion agent of the liquid phase when it dissolves in it, allowing that the reaction happens in a liquid phase rich in hydrogen; and supercritical carbon dioxide, a system where the temperature has a strong influence over the reaction and the pressure has a negative effect on the rate of the reaction, due to dilution and the competition of gas molecules with the reagents molecules for the catalyst. The optimal reaction condition was determined for the supercritical regime and kinetic data were obtained for both the sub and supercritical regimes.

Os albatrozes e petréis (Procellariiformes) são aves oceânicas e migratórias de grande interesse conservacionista. Neste trabalho foram estudadas duas classes de poluentes bastante conhecidos por afetarem negativamente as aves marinhas: os poluentes orgânicos persistentes e os plásticos. Bifenilos policlorados (PCBs) e pesticidas organoclorados foram detectados no tecido adiposo, fígado e músculo de oito espécies de Procellariiformes. Apesar da grande variabilidade intraespecífica nas concentrações, os perfis de PCBs e pesticidas organoclorados foram semelhantes entre os indíviduos, com predôminância de PCBs penta, hexa e heptaclorados e do p´p-DDE. A condição corporal se mostrou um fator importante na variação e redistribuição dos organoclorados nos tecidos das aves. As análises de isótopos estáveis de carbono e nitrogênio no fígado e músculo das aves mostraram que a dieta não foi suficiente para explicar as concentrações de organoclorados nas espécies estudadas e reforçaram a influência de fatores como idade, distribuição e especifidade da dieta na contaminação por estes compostos em aves marinhas. PCBs e pesticidas organoclorados foram detectados em pellets e fragmentos plásticos encontrados no trato digestório das aves estudadas, com perfis semelhantes aos encontrados nos tecidos dos Procellariiformes. A ocorrência de poluentes orgânicos em plásticos evidencia a capacidade destes de adsorver e transportar estes compostos e reforça o potencial dos plásticos como uma fonte adicional de contaminação para os animais que os ingerem, como as aves marinhas. / Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. The aim of the present study was to evaluate two classes of pollutants that negatively affect seabirds: persistent organic pollutants and plastics. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were detected in the adipose tissue, liver and muscle of eight species of Procellariiformes. Although organochlorine concentrations exhibited a high degree of intra-species variability, the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p´p-DDE. Body condition was an important factor in the variation and redistribution of organochlorine compounds in the tissues of the birds. Stable isotope analysis of carbon and nitrogen in the liver and muscle revealed that diet alone was insufficient to explain the organochlorine concentrations in the species studied, suggesting the influence of factors such as age, distribution and diet specificity regarding organochlorine contamination in seabirds. PCBs and OCPs were detected in plastic fragments and pellets found in the digestive tract of Procellariiformes, with profiles very similar to those found in the tissues of the birds. The occurrence of organic pollutants in plastics demonstrates their ability to adsorb and transport these compounds and underscores the potential of plastics as an additional source of contamination in organisms that ingest these products, such as seabirds.

The aim of this study was to investigate a potential impact of the old polychlorinated biphenyls (PCBs) dump on their occurrence in Bezdrevsky stream basin. Wastes, containing PCBs, were illegally stored in the area of ex-agrochemical factory in Lhenice village. Six localities were chosen for sampling by the method of integrative passive samplers SPMD, which provides more valuable information about contamination than commonly used grab samples. Passive samplers were exponated for 18 days in June 2017. The samples extraction was performed at the Laboratory of environmental chemistry and biochemistry (Faculty of fisheries and protection of waters), followed by clean up and preparation of these extracts for analysis with gas chromatograph coupled to tandem mass spectrometer (GC-MS/MS). Obtained data on PCBs amount in the samples were recalculated to their concentration in water. Concentration of seven indicator PCBs congeners (PCB 28 + 31, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 a PCB 180) was determined. These congeners are typical for technical PCBs mixtures which were produced in Czechoslovakia in the past. From their relative abundance, the potential source and an age of the contamination were estimated. Their total sum indicated significant exceedance of the limit only for the first locality, in the reservoir draining the dump area. There was found the concentration of 100 ng.l-1 of the 7 indicator PCBs sum. Concentrations at other localities complied with required limits and varied between hundredths to tenths of ng.l-1. In comparison with older data acquired from this area, the concentration at the first locality did not change, whereas PCBs concentration at the second and third locality downstream is currently lower than in past. Our data were compared to the latest data of PCBs concentrations in selected localities in CZ, which were received from Czech hydrometeorological intitute. From measured values can be stated, that the basin of Bezdrevsky stream and its fish pond system are not endangered by the presence of PCBs. Only two localities situated near the source of PCBs are comparable with localities in CZ which are influenced by the long term industry presence.

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