O crescente mercado dos produtos naturais, fomentado pelo interesse dos consumidores por alimentos que auxiliem a promoção da saúde, tem pressionado a indústria alimentícia na oferta por novos alimentos. Dentre estes alimentos, encontram-se os óleos vegetais extraídos a frio, reconhecidos por preservarem compostos bioativos característicos e, alguns deles, serem fontes de ácidos graxos (AG) essenciais. A categoria dos óleos e gorduras apresenta, dentre outros alimentos, uma importante fonte de exposição aos hidrocarbonetos policíclicos aromáticos (HPAs), um grupo de contaminantes químicos orgânicos, alguns com ação carcinogênica. Este trabalho teve como objetivo avaliar os óleos vegetais extraídos a frio quanto aos parâmetros de identidade, de qualidade e à ocorrência de HPAs. Foram avaliadas 40 amostras, dez de cada tipo (coco, cártamo, prímula e linhaça), de diferentes marcas, adquiridas no comércio da cidade de São Paulo. Foram realizados os ensaios de perfil de AG, índice de acidez, índice de peróxido, p-anisidina, valor total de oxidação (totox) e HPAs (benzo(a)antraceno, criseno, benzo(b)fluoranteno e benzo(a)pireno). Quanto aos AG, catorze óleos (35 por cento ) não apresentaram perfis de ácidos graxos característicos que os declarados em seus rótulos, incluindo um de coco, quatro de cártamo e nove de prímula. Os valores para acidez estavam inadequados em relação a legislação para três óleos de linhaça (7,5 por cento ). Para o peróxido, quatro óleos (10 por cento ) estavam acima do limite da legislação, sendo dois de linhaça e dois de prímula. Os valores de p-anisidina variaram de <LQ a 12,98, sendo o menor valor encontrado nas amostras de coco e o maior em uma de prímula, que apresentava um odor alterado. No ensaio de totox, 37,5% das amostras apresentaram valores acima da recomendação da literatura, especialmente os óleos de cártamo e prímula. Já para os HPAs, pelo menos um dos hidrocarbonetos analisados foi detectado em 97,5% das amostras avaliadas; três amostras de prímula (7,5%) apresentaram níveis acima do permitido pela Comunidade Européia para BaP e, para a soma dos 4 HPAs, oito óleos (20%) estavam em desacordo: dois de cártamo, quatro de prímula e dois de linhaça. Este trabalho expõe os problemas relacionados aos parâmetros de identidade, qualidade e contaminação dos óleos vegetais comercializados como extraídos a frio e reforçam a importância de um contínuo monitoramento destes produtos. / The natural product market growth, stimulated by the interest of consumers in foods that support health promotion, has encouraged the food industry to supply new kinds of foods. Among these are the cold-pressed vegetable oils, recognized by preserving characteristic bioactive compounds and, some of them, are sources of essential fatty acids (FA). The category of oils and fats owns, within others foods, an important source of exposure to polycyclic aromatic hydrocarbons (PAHs), a group of organic chemical contaminants, some of them with carcinogenic activity. This study aimed at evaluating cold-pressed vegetable oils in relation to the PAHs occurrence, as well as the quality and identity parameters. Forty samples being ten of each type (coconut oil, safflower oil, evening primrose oil and flaxseed oil) of distinct brands, which were acquired in different markets from São Paulo, were evaluated. Fatty acids profile, acid value, peroxide value, p-anisidine value, total oxidation value (totox) and PAHs (benzo(a)anthracene, chrysene, benzo(b)fluoranthene and benzo(a)pyrene) were analyzed. As for FA, fourteen oils (35 per cent ) showed different fatty acids profiles according to the ones on their labels, including one of coconut oil, four of safflower oils and nine of evening primrose oils. The acid values were unsuitable towards the legislation to three flaxseed oils (7.5 per cent ). As for peroxide values, four of the oils (10 per cent ) were above the legislation limit, including two of flaxseed oils and two of evening primrose ones. The p-anisidine values ranged from <LOQ to 12.98, being the smallest value found in the coconut oils samples and the biggest ones in an evening primrose oil, which featured an altered odor. In the totox analysis, 37,5% of the samples presented values above the normal pattern according to literature, mailly the safflower and theevening primrose oils. Regarding the PAHs, at least one of the analyzed hydrocarbons was detected in 97,5% of the samples; three of the primrose samples (7,5%) had levels above those allowed by the European Community for BaP. According to the sum of 4 PAHs, eight oils (20%) were in disagreement: two of safflower oils, four of evening primrose oils and two of flaxseed oils. This study exposes problems related to identity and quality parameters, contamination of vegetable oils marketed as cold-pressed. It also aims at reinforcing the importance of a continuous monitoring os these products.

Les hydrocarbures aromatiques polycycliques (HAP) sont des polluants organiques largement répandus dans l’environnement. Ils sont très fréquemment détectés dans les sols et sont principalement le produit d’une combustion incomplète de la matière organique. Etant toxiques et cancérigènes, de nombreuses études portant sur leur élimination des sols ont été massivement effectuées au cours des dernières années. Parmi tous les traitements disponibles pour traiter des sols contaminés par les HAP, les approches biologiques sont prometteuses car elles ont un impact limité, voire nul sur l’environnement. Cependant, leur efficacité est étroitement dépendante de nombreux facteurs difficiles à contrôler. L’objectif de cette thèse a été d’obtenir une connaissance plus précise concernant la dépollution biologique de sols contaminés par des HAP, en définissant à travers une série d‘expériences, les conditions les plus appropriées pour leur élimination principalement en termes de caractéristiques physiques et chimiques du sol, de la structure des HAP et leurs concentrations, la densité et la composition microbienne, le pH et l’humidité du sol et la disponibilité des nutriments. Les expériences réalisées dans cette thèse, sont basées sur le compostage de déchets organiques avec des sols contaminés par des HAP. L’ajout de matière organique vise à promouvoir la dégradation biologique simultanée des HAP et des déchets organiques frais en conditions contrôlées. Les résultats attendus de cette approche sont la dégradation des polluants en composés moins nocifs, en raison de la stimulation de l’activité des micro-organismes présents dans le sol ainsi que dans les déchets organiques apportés. Dans le but de comprendre l’influence des facteurs précédemment mentionnés, les expériences ont été menées sur un sol synthétique, artificiellement contaminé, ainsi que sur un sol contaminé provenant d’un site industriel identifié comme pollué par des HAP. Quatre types de déchets organiques frais ont été sélectionnés pour être ajoutés au sol artificiellement contaminé par des HAP. Les résultats ont montré que les boues activées étaient l’amendement organique le plus efficace par rapport au fumier de bufflonnes, aux déchets de cuisine et aux déchets organiques à base de légumes. Un taux d’élimination des HAP totaux supérieur à 60% a été atteint avec les boues activées. En outre, cette série d’expériences a prouvé que les conditions mésophiles étaient plus favorables que les conditions thermophiles, mais également que la teneur en azote, l’importance de la fraction soluble et les teneurs en protéines sont très importantes pour l’élimination des HAP. Sur la base de ces résultats, une série d’expériences a été menée sur un sol historiquement contaminé en apportant des quantités différentes de boues activées (ratio massique sol contaminé : boues activées variant de 1:2, 1:1 , 1:0,5 à 1:0). Contrairement aux résultats obtenus avec le sol artificiel, pour un sol naturellement contaminé, les amendements à base de boues activées n’ont pas stimulé l’élimination de HAP. Les meilleurs résultats ont été obtenu pour le sol non amendé par les boues activées (un rendement d’élimination des HAP totaux de 32% a été atteint en l’absence de boues activées, tandis qu'en présence d’un amendement à base de boues activées les meilleurs résultats ne dépassent pas 14% d’élimination des HAP totaux), cela prouve que la stimulation de micro-organismes pouvant dégrader les HAP est un facteur clé pour le succès du processus de dépollution biologique dans des conditions environnementales favorables / Polycyclic Aromatic Hydrocarbons (PAHs) are organic pollutants widely distributed in the environment and very frequently detected in soils as they are mainly produced from an incomplete combustion of organic matter at high temperature. They are toxic and even carcinogenic, therefore their removal from soils has been massively studied in the past years. Among all treatments suitable for treating soils contaminated by PAHs, biological ones are promising and challenging as they have a low or even no impact on the environment as well as their efficiency is tightly dependent on many factors not easy to control. The objective of this thesis has been to get more accurate knowledge on bioremediation of PAHs contaminated soils, by defining, through a series of experiments, the most suitable conditions for their biological remediation mainly in terms of physical and chemical soil characteristics, PAHs type and concentration, microbial density and composition, pH value, moisture content and availability of nutrients. The bioremediation experiments carried out in this thesis are based on landfarming as well as composting soil treatments and aimed at promoting the simultaneous biodegradation of PAHs and fresh organic wastes under controlled conditions. The expected result of this approach has been the conversion of organic pollutants into less harmful compounds, due to the activity of the microorganisms present in soil as well as in the organic waste added to soil. With the aim of deeply understanding the influence of the aforementioned factors on the bioremediation of PAHs contaminated soil, experiments were conducted on a synthetic soil, artificially contaminated, as well as on a real contaminated soil. In details, four different types of fresh organic waste were selected to be added to PAHs artificially contaminated synthetic soil and the results showed that centrifuged activated sewage sludge (SS) was the most effective organic amendment compared to buffalo manure (BM), food and kitchen waste (FKW) and fruit and vegetable waste (FVW). The removal efficiency of total PAHs reached with SS was actually a little higher than 60%. Furthermore, this set of experiments proved that mesophilic conditions were more performing than thermophilic conditions, as well as the content of nitrogen, soluble fraction and proteins played an important role in the PAHs removal. Based on the previous results, the next set of experiments was conducted on a real contaminated soil amended with different amounts of centrifuged activated SS (e.g. contaminated soil to SS mass ratios were 1:2, 1:1, 1:0.5 and 1:0 as wet weight basis). In contrast to results obtained with synthetic soil, in a real contaminated soil, SS amendment resulted in being not beneficial to PAHs removal. The best results were actually achieved where no SS was added (total PAHs removal efficiency of 32%, whereas with SS the best results showed a value of 14%), proving that the adaptation of microorganisms to PAHs is the key factor for the success of the bioremediation process coupled with setting favorable environmental conditions

In this thesis, I report the gas phase infrared spectra of some polycyclic aromatic hydrocarbons (PAHs) namely 1, 5-, 1, 6-, and 2, 6-dimethyl naphthalenes (DMNs); 2, 4-, 2, 6-, 2, 7-, and 2,8-dimethyl quinolines (DMQs); and 1, 9-, 2, 4-, and 3, 9-dimethyl phenanthrenes (DMPs) and diols such as 1, 2-ethylene glycol (1,2-EG) and 1, 4-butanediol (1,4-BD). Assignment of the IR spectra has been done with the help of DFT calculations followed by scaled quantum mechanical force field calculations. Chapter 1 gives a brief introduction to PAHs and diols. A brief survey of literature pertinent to their sources, their importance, experimental techniques for identification of PAHs and different conformers of diols and intramolecular interactions between the two hydroxyl groups in the diols are presented. The scope and motivation of the present investigation have been described at the end of the chapter. In Chapter 2, I have discussed all the methods used in carrying out this work. The details of the experimental FT IR set-up and quantum-chemical calculations employed in this work have been elaborated in this chapter. The subsequent chapters 3 - 5 deal with the experimental and theoretical results obtained for DMNs, DMQs, and DMPs. In chapter 3, infrared spectra of 1,5-, 1,6-, and 2,6-DMN have been described. The spectra have been recorded using a multi-pass gas cell coupled with Nexus-870 spectrometer (Thermonicolet, US). Qualitatively, spectral assignments have been made with the help of calculated doubly scaled (one scaling factor for the C-H stretching and another factor for the non C-H stretching frequencies) harmonic frequencies at the B3LYP/6-31G* level of theory. The spectral features to distinguish three different isomers of DMN have been identified. In chapter 4, IR spectra of 2,4-, 2,6-, 2,7-, and 2,8-DMQ in the gas phase have been recorded using a high resolution Vertex-70 (Bruker Optics, Germany) FT-IR spectrometer. DFT calculations have been carried out in order to get harmonic and anharmonic frequencies and their intensities at the B3LYP/6-31G* level of theory. Unambiguous assignments of IR bands could not be made with the help of anharmonic or selectively scaled harmonic frequencies. Therefore, scaled quantum mechanical (SQM) force field calculations were performed where force fields in local coordinates were scaled for getting frequencies in close agreement with experiment. Potential energy distributions (PEDs) of the normal modes in terms of the local coordinates of the molecule using a modified UMAT program in the QCPE package were also obtained in order to identify the nature of the fundamental vibration modes. In chapter 5, I have presented the gas phase IR spectra of 1,9-, 2,4-, and 3,9-DMP. The harmonic and anharmonic frequencies and their intensities were obtained at the B3LYP/6-31G* and B3LYP/6-311G** levels of theory. I have carried out SQM calculations for the assignment of the experimental frequencies in a similar fashion as was done for the DMQs. In chapter 6, IR spectra of two diols namely 1,2-ethylene glycol and 1,4-butane diol are reported and discussed. DFT calculations have been carried out for the harmonic fundamental frequencies and intensities at the experimental temperatures with 10 unique chosen conformers of the diols at the B3LYP/6-311++G** level of theory. Gas phase equilibrium population analysis has been done in order to generate the theoretical spectrum with the weighted average contributions from the 10 conformers to match the experimental spectrum. The hydrogen bond enthalpy, strength and nature have been investigated in details. From this experimental and theoretical studies, it has been concluded that the intramolecular hydrogen bond is absent in 1,2-EG at ordinary temperatures whereas it is present in 1,4-BD. vi Chapter 7 is the concluding chapter where the main work done in this thesis is summarized and future direction is presented.

Oil spills, especially in water have happened throughout the years. The consequences from this kind of incident have always been a threat to marine life and take a lot of money and time to clean up. The forensic investigations of oil usually focus on oil spill in water, however, this kind of investigation can be applied on more areas, such as in sexual offense cases and arson. The oil from the crime scene and the oil from the suspected source are analyzed and compared to each other to see if the compositions match. The aim of this thesis was to optimize the clean-up process of heavy fuel oil (HFO) using solid-phase extraction (SPE) according to the European Committee for standardization (CEN) 15522-2 method. HFOs are black oils, containing particles and soot which will decrease injector performance. Thus, a cleanup procedure is attractive when analyzing such samples. The three factors of optimization in this study were elution volumes, solvents, and SPE sorbents.The SPE method used in this study was to use the cartridges as a filter; therefore, the samples were both loaded and eluted with an organic solvent, in this case dichloromethane (DCM) or dichloromethane/heptane (DCM/Hp). The gas chromatography mass spectrometry (GC-MS) analysis method used is described in Annex B in the CEN 15522-2 method.Concluding, increasing the eluent volume did not indicate improvement on the extraction method. In terms of the solvents, both dichloromethane and dichloromethane/heptane showed similar results. The percentage weathering plots (PW-plots) showed that the SPE sorbents (dual layer florisil/Na2SO4, florisil and silica gel sorbents) worked similar. The overall conclusion from this thesis work was that further optimization must be made before implementing the method.

Les hydrocarbures aromatiques polycycliques (HAPs), tels que le benzo(a)pyrène (B[a]P), sont des contaminants environnementaux ubiquistes générés lors de la combustion de matière organique. Ces composés ont été associés au développement d'effets toxiques sur la santé humaine, notamment des effets cancérigènes et immunotoxiques, principalement liés à l'activation du récepteur aux hydrocarbures aromatiques (RAh). Parmi les cellules du système immunitaire, les lymphocytes T apparaissent comme des cibles majeures des HAPs. Des résultats antérieurs, obtenus au laboratoire, ont montré que l'activation des lymphocytes T humains en culture primaire conduit à l’augmentation de l'expression et de la fonction du RAh, suggérant la capacité accrue de ces cellules à répondre à une exposition aux HAPs. Nos objectifs sont : (1) de déterminer les effets du B[a]P sur les profils d'expression génique dans les lymphocytes humains normaux en utilisant des approches à haut débit telle que l'analyse transcriptomique sur puce à ADN, (2) d’évaluer les effets génotoxiques et immunotoxiques du B[a]P en mesurant respectivement les dommages à l'ADN induits et leurs actions immunosuppressives et (3) d’analyser la modulation de ces effets en présence d'autres HAPs. Notre travail identifie les lymphocytes T humains normaux comme un bon modèle pour étudier les effets génotoxiques et immunotoxiques des HAPs, et pour prédire les problèmes de santé humaine liés à l’exposition à ces contaminants. Il permet également de mieux comprendre la régulation par les HAPs de la réponse immune et propose de nouveaux biomarqueurs potentiels de l'exposition à ces contaminants environnementaux. / Polycyclic aromatic hydrocarbons (PAHs), such as benzo(a)pyrene (B[a]P), are ubiquitous environmental contaminants generated during organic matter combustion. These compounds have been associated with the development of toxic effects on human health, including carcinogenic and immunotoxic effects, mainly related to Aryl hydrocarbon Receptor (AhR) activation. Among the immune system cells, T lymphocytes appear as major targets of PAHs. Previous results, obtained in the laboratory, have shown that activation of primary human T lymphocytes leads to a functional AhR expression increase, suggesting their ability to respond to PAH exposure. Our specific aims are: (1) to determine the effects of B[a]P on gene expression profiles in human normal lymphocytes by using large-scale approaches such as microarray-based transcriptome analysis, (2) to monitor the genotoxic and immunotoxic effects of B[a]P by measuring DNA damage and immunosuppressive actions, respectively and, (3) to analyze the modulation of these effects by the presence of other PAHs. Our work propose primary cultures of activated human T lymphocytes as a good model for studying both genotoxic and immunotoxic effects of environmental contaminants such as PAHs and predicting human health issues. It also gains a comprehensive insight into the immune response regulation after PAH exposure and provides potential new biomarkers of exposure to these environmental contaminants.

Soils contaminated by hydrophobic organic pollutants like polycyclic aromatic hydrocarbons (PAHs) are a common concern since they are extremely difficult to remove and their potential toxicological impacts are significant. As an alternative to traditional thermal or physical treatments, soil washing and soil flushing processes appear to be conceivable and efficient approaches, especially for higher level of pollution. However, the treatment of highly loaded soil washing/flushing solutions is another challenge to overcome. In that way, a new integrated approach is suggested: soil washing/flushing processes combined to an electrochemical advanced oxidation process (EAOP) in a combination with a recirculation loop (to save extracting agents) and/or a biological post-treatment step (to minimize energy cost).Extraction efficiency of the extracting agent like hydroxypropyl-beta-cyclodextrin (HPCD) is compared to the traditional non-ionic surfactant Tween 80 in synthetic and real soil washing solutions. A new simple fluorescent sensitive and selective quantification method is developed to monitor Tween 80 oxidation. Two EAOPs were compared: electro-Fenton (EF) and anodic oxidation (AO). Platinum (Pt) (in EF process) and boron doped diamond (BDD) (in both treatment) anodes are the respective electrodes employed to recycle effluents and to consider a biological post-treatment, respectively. Regarding the extracting agent recovery, the biodegradability evolution of effluent and the energy consumption (in kWh (kgTOC)-1) during EAOP, HPCD is more advantageous than Tween 80. However, in terms of extraction efficiency, costs of extracting agents and impact on soil respirometry, Tween 80 is much more efficient. By considering all these advantages and drawbacks, Tween 80 could still appear to be the best option

The aim of the study was to determine the 13 health risk PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene, ideno(1,2,3-cd)perylene and coronene; c-PAU highlighted) in the fractions of size-segregated aerosol of the urban air in Ostrava (2012, 2014) and Mlada Boleslav (2013) at low temperatures in winter, and to verify experimentally a sampling artifact, i.e., to quantify PAHs in the gas phase. For the particle size separation high-volume cascade impactor Hi-Vol BGI 900 was used. PAHs were determined by HPLC-FLD/PDA. In Ostrava in 2012 during the winter inversion (up to -25 řC), mean concentration of 13 PAHs in aerosol was 432 ng.m-3 ; in fraction 10 - 1 µm 119 ng.m-3 , 1 - 0,5 µm 185 ng.m-3 , 0,5 - 0,17 µm 91 ng.m-3 , in fraction < 0,17 µm 37 ng.m-3 and in the gaseous phase of min. 40 ng.m-3 . In the most unfavorable day 2. 2. 2012 (-18.6 ř C) reached the 24-hour average of 13 PAHs 890 ng.m-3 , the sum of carcinogenic PAHs 237 ng.m-3 and benzo(a)pyrene 32.3 ng.m-3 . An irregular and different decline of PAHs concentrations after inversion was measured: in fraction 1 - 10 µm 2.8 times, 0.5 - 1 µm 4.2 times, 0.5 - 0.17 µm 4 times and for <0.17 µm up to 7.6 times....

L'essor que connaît aujourd'hui la gestion intégrée des eaux pluviales s'accompagne d'un recours croissant à des techniques favorisant l'infiltration de l'eau “à la source”, disséminées sur des bassins versants urbains. Néanmoins, de telles pratiques suscitent des interrogations sur la capacité du sol à jouer le rôle de “filtre” vis-à-vis des polluants présents dans le ruissellement. Ces travaux de thèse s'intéressent à la contamination du sol par les métaux et les hydrocarbures aromatiques polycycliques (HAP) dans ces dispositifs, avec trois objectifs : (i) évaluer les niveaux et l'étendue spatiale de la contamination, (ii) mieux comprendre les mécanismes qui gouvernent le devenir de ces contaminants dans le sol des ouvrages, et (iii) proposer des recommandations sur la conception et la maintenance de ces installations, afin de leur assurer un fonctionnement épuratoire durable.La première partie du travail consiste en une série d'investigations expérimentales sur dix sites d'étude aux caractéristiques contrastées, en service depuis plus de dix ans. Cette phase donne lieu à des cartographies de la contamination superficielle en éléments traces métalliques, puis à des profils verticaux de métaux et HAP, accompagnés de différentes variables explicatives. La distribution spatiale des métaux en surface, qui est toujours structurée autour de la zone d'arrivée de l'eau, porte la signature du fonctionnement hydraulique réel des dispositifs, et révèle le caractère non-uniforme de l'infiltration lors des événements pluvieux courants, qui représentent la plus grande partie du flux polluant à l'échelle annuelle. Dans la zone la plus contaminée des ouvrages, métaux et HAP présentent un enrichissement significatif sur 10 à 40 centimètres de profondeur. La rétention des contaminants résulte de la combinaison de processus physico-chimiques (adsorption) et mécaniques (sédimentation et filtration) ; leur importance relative peut être quantifiée grâce au déficit de zirconium dans le sédiment urbain par rapport au bruit de fond géochimique local. La variabilité inter-sites des niveaux de contamination s'explique à la fois par les capacités de rétention du sol et par les flux de polluants issus du bassin versant d'apport. Bien que les teneurs de surface excèdent, sur certains sites, les seuils internationaux de remédiation du sol pour des espaces “multifonctionnels”, la zone concernée représente — latéralement et verticalement — une région assez limitée dans les ouvrages.La seconde partie de la thèse consiste en une approche de modélisation, dont la finalité est de décrire l'évolution à long terme de la contamination du sol, et d'évaluer l'incidence de différentes pratiques de conception ou de gestion. Une analyse de sensibilité est d'abord mise en œuvre afin d'identifier les “éléments-clés” dans la description du système, et d'orienter le choix du modèle. Les résultats montrent qu'une mauvaise estimation de la dispersivité ou de l'isotherme d'adsorption du sol est susceptible de biaiser significativement la prévision des profils de contamination. Dans la suite du travail, on propose une méthode visant à décrire l'infiltration non-uniforme et la filtration des polluants particulaires. Le modèle ainsi construit est validé via une comparaison entre mesures et simulations sur l'un des sites d'étude faisant l'objet d'une nouvelle caractérisation approfondie. Enfin, une analyse de scénarios illustre les bénéfices d'un amendement de l'horizon superficiel par un matériau adsorbant, ainsi que d'une répartition homogène des flux d'eau en surface, en matière de durée de vie des installations et de fréquence d'intervention. / Sustainable Urban Drainage Systems (SUDS) are increasingly used for stormwater management. However, the generalization of runoff infiltration in urban watersheds raises some concerns regarding the soil's ability to retain ubiquitous micropollutants. The present work addresses soil contamination by trace metals and polycyclic aromatic hydrocarbons (PAHs) in such infiltration devices, with the aims of: (i) appraising the levels and spatial extent of soil contamination, (ii) better understanding the mechanisms which govern the fate of contaminants in these systems, and (iii) identifying design and maintenance guidelines which may enhance long-term pollutant control through SUDS.The first part of the study consists in a series of experimental investigations in ten contrasting study sites, which have been in operation for more than ten years. The two-stage methodology successively leads to cartographies of metal contamination in the surface soil, and vertical profiles of metal and PAH concentrations, along with different explanatory variables. The spatial distribution of trace metals in the upper horizon displays a systematic structure with respect to the inflow area, and bears the time-integrated signature of the infiltration fluxes and flow pathways at the surface. In the most contaminated zone of the facilities, a significant enrichment of metals and PAHs is detectable until 10 to 40 cm depth. Contaminant retention results from the combination of different physicochemical and mechanical processes (resp. sorption and sedimentation/filtration), the contribution of which can be assessed via the zirconium deficit in urban sediment in comparison to the soil's geochemical background. The inter-site variability of contamination levels is attributable to (i) differences in the soil's retention capacities, and (ii) differences in pollutant loads from the watershed. Although surface contents may exceed intervention thresholds for “multi-functional” spaces in several study sites, the area which would require soil remediation is laterally and vertically limited.These experimental assessments are complemented by a modelling approach, to describe the long-term evolution of soil contamination, and to evaluate the effect of various SUDS designs and maintenance operations. A sensitivity analysis is first carried out so as to identify the “key elements” in the system description: the results show that a wrong estimation of the soil's dispersivity or sorption isotherm is likely to induce significant biases in the predicted contamination profiles. A method is then proposed to describe non-uniform water infiltration fluxes, and the filtration of particle-bound contaminants. The model is validated via a comparison between measured and predicted metal profiles in one of the study sites, where a comprehensive soil characterization is undertaken. Finally, a “scenario analysis” illustrates the benefits of (i) using soil enrichment products with enhanced sorption capacities, and (ii) facilitating water spreading at the surface, in terms of “lifespan” of the devices and maintenance requirements.

Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1 JulianaPSDP_DISSERT.pdf: 1777680 bytes, checksum: 11814e53360b103c7198cf617f2a583c (MD5) Previous issue date: 2010-07-06 / The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive / O presente trabalho ? dirigido ao tratamento de ?gua produzida de petr?leo usando uma tecnologia eletroqu?mica. A ?gua produzida ? um dos principais res?duos gerados durante o processo de explora??o e produ??o na ind?stria petrol?fera, onde corresponde a 98 % de todos os efluentes gerados. V?rias metodologias est?o sendo estudadas visando o tratamento desse efluente, dentre elas est?o os processos biol?gicos, os processos de oxida??o avan?ados (POAs), tratamentos eletroqu?micos como eletrooxida??o, eletrocoagula??o, eletroflota??o e eletroredu??o. Esse trabalho mostra a aplica??o da tecnologia de eletrooxida??o no tratamento da ?gua produzida, pois se trata de uma t?cnica com alta compatibilidade ambiental, onde atrav?s da a??o do pr?prio el?tron, as subst?ncias t?xicas e nocivas ao meio ambiente podem ser removidas ou transformadas atrav?s de rea??es de ?xido-redu??o em subst?ncias menos t?xicas. Para isso, foi utilizado efluente sint?tico contendo uma mistura de H2SO4 0,5M e de 16 hidrocarbonetos polic?clicos arom?ticos (HPAs), que s?o: naftaleno, acenaftileno, acenafteno, fluoreno, fenantreno, antraceno, fluoranteno, pireno, benzo(a)antraceno, criseno, benzo(b)fluoranteno, benzo(k)fluoranteno, benzo(a)pireno, indeno(1,2,3-cd)pireno, dibenzo(a,h)antraceno, benzo(g,h,i)perileno. Utilizou-se o processo de oxida??o eletroqu?mica com um reator eletroqu?mico em batelada contendo um par de eletrodos paralelos, acoplados a uma fonte de corrente cont?nua e usando um agitador magn?tico para favorecer o transporte de massa na solu??o sint?tica. Como material an?dico utilizou-se um eletrodo de ?nodo dimensionalmente est?vel (DSA), constitu?do de Ti/Pt, enquanto o material cat?dico foi o Ti. Para detec??o e quantifica??o dos HPAs utilizou ? t?cnica de cromatografia gasosa acoplada a espectrometria de massa (CG - EM), onde o efluente foi analisado antes e ap?s o tratamento eletroqu?mico. Os resultados se mostraram eficazes, obtendo-se remo??es significativas dos HPAs superiores a 80%. Como indicador da viabilidade econ?mica do tratamento eletroqu?mico foram analisados os consumos energ?ticos do processo para cada hora do tratamento eletroqu?mico com base no valor kWh cobrado pela ANEEL. Os custos dos tratamentos desta pesquisa foram bastantes atrativos

Polycyclic aromatic hydrocarbons (PAHs) are pollutants of great concern due to their toxicity, ubiquitous distribution and environmental persistence. Generally, the PAHs are found as part of complex mixtures such as crude oil and derivatives, and mineral coal. Mismanagement during industrial operations, and accidental spills result in the contamination of wide areas with potential risk for the public health and negative impact in the local economy. Nowadays, there is a considerable interest in the use of biological procedures to clean up polluted environments because of their pollutant removal efficiency, feasibility and associated low cost. Bioremediation experiences are based on the ability that microorganisms (bacteria, algae and fungi) possess in degrading a wide range of pollutants, including PAHs containing from two to five aromatic rings. The microbial biodegradation of low molecular weight (LMW) PAHs has been extensively studied revealing a variety of bacteria capable to efficiently degrade these pollutants. The studies with high molecular weight (HMW) PAHs, more recalcitrant and with higher toxicity, indicate that in soil environments this compounds are generally degraded by members of the group Actinobacteria. However, little is known about HMW-PAH degradation in marine environments. Recent studies carried out with marine consortia and isolates have identified a few genera as PAHs degraders in sea waters, but no associations have been established between pyrene degradation and actinobacteria in such environments. Here, with the study of a pyrene microbial marine consortium, we provide the first evidence on the key role of actinobacteria in the removal of pyrene from polluted marine shorelines. Moreover, the detailed analysis of the community structure of the microbial consortium have revealed the presence of a bacterial strain not classifiable in the previously described genus, that have been isolated, thoroughly characterized and proposed as a type strain of a new genus and species. Bioremediation experiences do not always produce the desired results. PAHs are usually degraded until certain limit after which degradation is hardly observed. This phenomenon may be mainly caused by the low bioavailiability and limited concentration of nutrients. PAHs are usually found in non-aqueous phase liquids (NAPLs), which results in a slow partition of these components into the aqueous phase and their persistence in to the environment for long periods. In order to enhance microbial degradation and reduce the residual PAH concentration in polluted environments, we have conducted an experiment in which the effect of an oleophilic fertilizer has been evaluated. We also have targeted the possible nutritional deficiencies during bioremediation and have examined the biodegradation of PAHs and potential accumulation of partially oxidized metabolites, more available and toxic than their parent PAHs. Finally, we have evaluated the efficiency of sunflower rhizosphere in PAH removal from polluted soils that have undergone extensive remediation but still contain intolerable levels of pollutants. The results indicate that the sunflower rhizosphere enhance the removal of PAHs by promoting the selective growth of degradative bacteria, incrementing the bioaccesibility and possible favouring the degrading processes through specific mechanism associated with the composition of the roots exudates. These results represent a promising alternative for increasing bioremediation in a sustainable and cost-efficient manner. / Los hidrocarburos aromáticos policíclicos son un grupo de contaminantes que suscitan gran preocupación debido a su toxicidad, amplia distribución y persistencia en el medio ambiente. Generalmente, los HAPs se encuentran formando parte de mezclas complejas como crudos de petróleo, carbón mineral y derivados. La mala gestión durante las operaciones industriales, y los vertidos accidentales causan amplias áreas contaminadas que conllevan un importante riesgo para la salud pública junto con un impacto negativo en la economía local. Actualmente, hay un notable interés en el uso de procedimientos biológicos para descontaminar emplazamientos debido a la eficiencia en la eliminación, viabilidad y bajo coste asociado de estos métodos. Las experiencias de biorremediación se basan en la capacidad de los microorganismos (bacterias, algas y hongos) de degradar una amplia variedad de contaminantes, incluyendo HAPs. La degradación microbiana de HAPs de bajo peso molecular ha sido ampliamente estudiada revelando numerosas bacterias capaces de eliminar eficientemente estos compuestos. Los estudios realizados con HAPs de alto peso molecular, más recalcitrantes y con mayor toxicidad, han mostrado que en suelos la degradación de estos compuestos es principalmente llevada a cabo por miembros del grupo Actinobacteria. Sin embargo, se desconoce la degradación de HAPs de elevado peso molecular en ambientes marinos. Estudios recientes llevados a cabo en consorcios marinos han identificado algunos géneros degradadores de HAPs en agua de mar, pero no se han establecido asociaciones entre el pireno y actinobacterias. Aquí, con el estudio del consorcio marino degradador de pireno, nosotros proveemos la primera evidencia del papel de las actinobacterias en la eliminación del pireno de costas marinas. Además, el análisis de la estructura de la comunidad bacteriana nos reveló la presencia de una cepa no clasificable en los géneros previamente descritos, que fue aislada, profundamente caracterizada y propuesta como cepa tipo de un nuevo género y especie. Las experiencias de biorremediación no siempre producen los resultados deseados. A menudo. los HAPs son degradados hasta cierto límite tras el cual la degradación apenas es observada. Este fenómeno puede ser causado principalmente por la baja disponibilidad y limitación de nutrientes. Los HAPs generalmente se encuentran formando parte de fases líquidas no acuosas (FLNAs), lo que resulta en una lenta partición de estos compuestos hacia la fase acuosa y por tanto en una persistencia medioambiental. Con el fin de incrementar la degradación microbiana y reducir la concentración residual de los HAPs en ambientes contaminados, se realizó un experimento en el cual se evaluaba el efecto de un fertilizante oleofílico. También se examinaron las posibles deficiencias nutricionales y la acumulación de metabolitos parcialmente oxidados resultantes de la degradación, los cuales son más disponibles y tóxicos que sus parentales. Finalmente, hemos evaluado la eficiencia de la rizosfera de girasol en la eliminación de HAPs de suelos contaminados con HAPs que han sido sometidos a una extensiva remediación, pero que contienen niveles inaceptables de HAPs. Los resultados indican que la rizosfera de girasol aumentó la eliminación de HAPs promoviendo el crecimiento selectivo de bacterias degradadoras y favoreciendo los procesos de degradación a través de mecanismos asociados con la composición de los exudados. Los resultados representan por tanto una alternativa prometedora para potenciar la biorremediación de una manera sostenible y rentable.