Firefighters and asphalt pavers are exposed to polycyclic aromatic hydrocarbons (PAHs) during various work activities. The purpose of this study was to evaluate urinary PAH levels and compare these bio-monitoring levels among firefighters, asphalt pavers, and non-occupationally exposed individuals. The National Institute of Standards and Technology (NIST) urinary PAH levels were used for non-occupationally exposed controls. When compared to the NIST standard for smokers and non-smokers, firefighters demonstrated statistically significant differences in urinary concentration differences for the following metabolites: 2-OH-fluorene, 3-OH-fluorene and 1-OH-pyrene, which were lower in firefighters than the NIST mean for smokers. 1-OH-phenanthrene, 2-OH-phenanthrene and 3-OH-phenanthrene were higher among world trade center exposed firefighters than the NIST mean for smokers. When firefighters were compared to the NIST non-smoker standard, firefighters demonstrated elevated levels in all tested PAH biomarkers due to a mixture of smokers and non-smokers in the firefighter cohort. Asphalt workers had statistically significant higher urinary concentration elevations in 2-OH-fluorene, 1-OH-phenanthrene and 3-OH-phenanthrene as compared to the NIST smoker mean. When asphalt pavers were compared to the NIST non-smoker mean, asphalt pavers had statistically significant increases in all tested PAH biomarkers, with the exception of 2-OH-phenanthrene. While firefighters did not demonstrate a substantial change in urinary PAH metabolite levels compared to control populations of smokers and non-smokers, asphalt pavers experienced concentrations that were in some cases increased by orders of magnitude compared to NIST controls. Future research may be needed to evaluate any potential health risk posted to occupational exposed asphalt pavers.

L'étude des surpressions de fluide et de fracturation hydraulique des roches mères peut nous renseigner sur les mécanismes de génération qui en sont à l'origine. Ces dernières années, l'intérêt pour ces phénomènes s'est largement accru, notamment sous l'influence des sociétés pétrolières qui exploitent les ressources non-conventionnelles au cœur des problèmes énergétiques actuels. Dans ce travail de thèse, nous avons choisi deux approches différentes pour l'étude de ces mécanismes : (1) des exemples de cas géologiques naturels, et (2) le développement de la modélisation analogique. Ainsi, nous montrons que ces phénomènes sont très répandus au sein des bassins sédimentaires et que leurs manifestations s'expriment notamment par la génération de veines fibreuses parallèles à la stratification de la roche (beef), mais également par la formation de veines d'hydrocarbures solides (bitume). Nous démontrons également que les surpressions de fluides peuvent profondément changer le style de déformation d'un bassin sédimentaire par la génération de niveaux de décollement localisés au sein même des roches mères. Enfin, à l'aide de la modélisation analogique, nous avons pu identifier les mécanismes à l'origine des surpressions de fluide et de la fracturation hydraulique. En effet, lors de la génération d'hydrocarbures la transformation de solide à liquide de la matière organique conduit à la compaction chimique des sédiments. Par un mécanisme de transfert de charge lors de ce processus, ainsi que par l'accroissement de volume associé, des surpressions de fluides se développent et atteignent des pressions lithostatiques, capables de fracturer hydrauliquement les roches. / The study of fluid overpressures and hydraulic fracturing in source rocks can help us to understand the mechanisms, which are responsable for these phenomena. During the last few years, the interest in such processes has highly grown, especially through the influence of petroleum companies, which extract hydrocarbons from unconventional reservoirs. In this work, we have chosen to develop two different approaches for the study of these mechanisms: (1) field studies and (2) physical modelling. Thereby, we show that fluid overpressures and hydraulic fracturing are common in sedimentary basins worldwide. Bedding-parallel fibrous veins (beef) and solid hydrocarbon veins (bitumen) are the resulting structures. We also show that fluid overpressures can highly affect the deformation style in sedimentary basins, especially by causing thrust-detachments within source rocks. By the using of a new physcial modelling technique, we have identified the mechanisms, which are responsible for fluid overpressures and hydraulic fracturing. Indeed, during hydrocarbon generation, the solid organic matter becomes liquid, which leads to chemical compaction of the sediment. By a mechanism of load transfer, fluid overpressures rise to lithostatic values. However, volume changes also contribute, and are able to induce hydraulic fractures in the rocks.

Setenta e três fungos representantes de grupos taxonômicos distintos, isolados de cnidários, coletados no litoral norte do estado de São Paulo, foram submetidos ao teste de descoloração do corante RBBR e ao teste de MIC. Treze fungos selecionados no teste de descoloração foram submetidos ao teste de degradação de pireno e benzo[a]pireno. Sete fungos mostraram resultados satisfatórios de degradação, entretanto, o fungo Aspergillus sulphureus (8.2A) apresentou os melhores resultados: degradou 99,7% de pireno e 73,6% de benzo[a]pireno. Com relação ao teste de MIC, 21 isolados inibiram o crescimento das bactérias: B. subtillis; P. aeruginosa, S.aureus, E. coli EPEC e V. parahaemolyticus. Penicillium sp. (12.12) apresentou o melhor resultado (0,0078 mg/mL). Os 23 isolados que apresentaram potencial biotecnológico foram caracterizados taxonomicamente. Os resultados do presente trabalho sugerem que fungos filamentosos associados a cnidários possuem potencial para aplicação biotecnológica, em particular para biorremediação de ambientes marinhos contaminados com HPAs. / Seventy three fungi representatives of distinct taxonomic groups, isolated from cnidarians collected from north coast of São Paulo State, were submitted to RBBR dye decolorization tests and to MIC. Thirteen fungal selected from the decolorization test were submitted to pyrene and benzo[a]pyrene degradation assays. Seven fungi showed satisfactory PAH degradation results. Among them Aspergillus sulphureus (8.2A) presented the best results degrading pyrene (99.7%) and benzo[a]pyrene (73.6%). Regarding the MIC experiments, 21 isolates were able to inhibit the growth of B. subtilis, P. aeruginosa, S. aureus, E. coli EPEC and V. parahaemolyticus. Penicillium sp. (12.12) presented the best result (0,0078 mg/mL). The 23 isolates that showed potential biotechnologic were taxonomically characterized. Results derived from the present work suggest that cnidarians-derived filamentous fungi have a great potential for biotechnological application, in particular on bioremediation of marine environments contaminated by PAHs.

[EN] Social impact assessment (SIA) is a part of environmental impact assessment (EIA), which is characterized by a high level of uncertainty and the subjective aspects that are presents in the methods used during its conduction. In addition, environmental conflict analysis (ECA) has become a key factor for the viability of projects and welfare of affected populations. In this thesis, an integrated method for SIA and ECA is proposed, by the combination of the grey clustering method and the entropy-weight method. SIA was performed using the grey clustering method, which enables qualitative information coming from a stakeholder group to be quantified. In turn, ECA was performed using the entropy-weight method, which identifies the criteria in which there is greater divergence between stakeholder groups, thus enabling to establish measures to prevent potential environmental conflicts. Then, in order to apply and test the proposed integrated method, two case studies were conducted. The first case study was a mining project in northern Peru. In this study, three stakeholder groups and seven criteria were identified. The results revealed that for the urban population group and the rural population group, the project would have a positive and negative social impact, respectively. For the group of specialists the project would have a normal social impact. It was also noted that the criteria most likely to generate environmental conflicts in order of importance were: access to drinking water, poverty, GDP per capita, and employment. The second case study considered was a hydrocarbon exploration project located in the Gulf of Valencia, Spain. In this study, four stakeholder groups and four criteria were identified. The results revealed that for the group of specialists the project would have a negative social impact, and contrary perceptions were shown between the group of those directly affected by the project and the group of citizens in favour. It was also noted that the criteria most likely to generate environmental conflict were the percentage of unemployment and GDP per capita. The proposed integrated method in this thesis showed great potential on the studied cases, and could be applied to other contexts and other projects, such as water resources management, industrial projects, construction projects, and to measure social impact and prevent conflicts during the implementation of government policies and programs. / [ES] La evaluación del impacto social (SIA) forma parte de la evaluación de impacto ambiental (EIA), y está caracterizada por su alto nivel de incertidumbre, y por los aspectos subjetivos presentes en los métodos usados para su realización. Por otro lado, el análisis del conflicto ambiental (ECA) se ha convertido en un factor clave para la viabilidad de los proyectos y el bienestar de la población afectada. En esta tesis, se propone un método integrado para la SIA y el ECA, mediante la combinación de los métodos grey clustering y entropy-weight. La SIA fue desarrollada usando el método grey clustering, el cual permite cuantificar la información cualitativa recogida de los grupos de interés o stakeholders. Sucesivamente, el ECA fue realizado usando el método entropy-weight, el cual identifica los criterios en los cuales existe gran divergencia entre los grupos de interés, permitiendo así establecer medidas para prevenir potenciales conflictos ambientales. Luego, con el fin de aplicar y testear el método integrado propuesto fueron realizados dos casos de estudio. El primer caso de estudio fue un proyecto minero ubicado en el norte de Perú. En este estudio se identificaron tres grupos de interés y siete criterios. Los resultados revelaron que para el grupo población urbana y el grupo población rural, el proyecto tendría un impacto social positivo y negativo, respectivamente. Para el grupo de los especialistas el proyecto tendría un impacto social normal. También fue notado que los criterios más probables de generar conflicto ambiental en orden de importancia fueron: acceso al agua potable, pobreza, PIB per cápita, y empleo. El segundo caso de estudio considerado fue un proyecto de exploración de hidrocarburos ubicado en el Golfo de Valencia, España. En este estudio se identificaron cuatro grupos de interés y cuatro criterios. Los resultados revelaron que para el grupo de los especialistas el proyecto tendría un impacto social negativo, y contrarias percepciones se encontraron entre el grupo de los directamente afectados y el grupo de los ciudadanos a favor. También fue notado que los criterios más probables de generar conflicto ambiental fueron el porcentaje de desempleo y el PIB per cápita. El método integrado propuesto en esta tesis mostró un gran potencial sobre los casos estudiados, y podría ser aplicado a otros contextos y otros tipos de proyectos, tales como gestión de recursos hídricos, proyectos industriales, proyectos de construcción de obras públicas, y para medir el impacto social y prevenir conflictos durante la aplicación de políticas y programas gubernamentales. / [CAT] L'avaluació de l'impacte social (SIA) és una part de l'avaluació de l'impacte ambiental (EIA), la qual està caracteritzada pel seu alt nivell d'incertitud i els aspectes subjectius presents en els mètodes amprats durant la seua conducció. A més, la anàlisis del conflicte ambiental (ECA) s'ha convertit en un factor clau per a la viabilitat dels projectes i el benestar de la població afectada. En esta tesis es proposa un mètode integrat per a l'avaluació de l'impacte social i la anàlisis del conflicte ambiental, mitjançant la combinació del mètode grey clustering i el mètode entropy-weight. L'avaluació de l'impacte social ha segut realitzada usant el mètode grey clustering, el qual permet que la informació qualitativa arreplegada dels grups d'interès siga quantificada. Successivament, la anàlisis del conflicte ambiental ha segut realitzada usant el mètode entropy-weight, el qual identifica els criteris en els quals existeix gran divergència entre els grups d'interès, la qual cosa permet establir mides per a prevenir conflictes ambientals potencials. Després, amb la finalitat d'aplicar i testejar el mètode integrat proposat han segut realitzats dos casos d'estudi. El primer d'ells ha segut un projecte miner al nord de Perú. En aquest estudi, tres grups d'interès i set criteris foren identificats. Els resultats revelaren que per al grup població-urbana i el grup població-rural, el projecte experimentaria un positiu i un negatiu impacte social respectivament. Per al grup dels especialistes el projecte tindria un impacte social normal. Per altra banda també va ser reconegut que els criteris més probables de generar conflicte ambiental en orde d'importància foren: accés a l'aigua potable, pobresa, PIB per càpita, i ofici. El segon cas d'estudi considerat va ser un projecte d'exploració d'hidrocarburs ubicat al Golf de València, Espanya. En este estudi, quatre grups d'interès i quatre criteris foren identificats. Els resultats revelaren que per al grup dels especialistes el projecte tindria un impacte social negatiu, mentre que entre el grup dels directament afectats i el grup dels ciutadans a favor es mostraren percepcions contraries. Va ser també reconegut que els criteris més probables de generar conflicte ambiental foren el percentatge de desocupació i el PIB per càpita. El mètode integrat proposat en aquesta tesis mostra un gran potencial sobre els casos estudiats, i pot ser aplicat a altres contexts i altres tipus de projectes com gestió de recursos hídrics, projectes industrials i projectes de construcció d'obres públiques. A més pot fer-se servir per mesurar l'impacte social i prevenir conflictes durant l'aplicació de polítiques i programes governamentals. / Delgado Villanueva, KA. (2016). Methodological proposal for social impact assessment and environmental conflict analysis [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/64063 / TESIS

One antiaromatic polycyclic hydrocarbon (PH) with and without solubilizing tert-butyl substituents, namely s-indaceno[2,1-a:6,5-a′]dipyrene (IDPs), has been synthesized by a four-step protocol. The IDPs represent the longitudinal, peri-extension of the indeno[1,2-b]fluorene skeleton towards a planar 40 π-electron system. Their structures were unambiguously confirmed by X-ray crystallographic analysis. The optoelectronic properties were studied by UV/vis absorption spectroscopy and cyclic voltammetry. These studies revealed that peri-fusion renders the IDP derivatives with a narrow optical energy gap of 1.8 eV. The maximum absorption of IDPs is shifted by 160 nm compared to the parent indenofluorene. Two quasi-reversible oxidation as well as reduction steps indicate an excellent redox behavior attributed to the antiaromatic core. Formation of the radical cation and the dication was monitored by UV/vis absorption spectroscopy during titration experiments. Notably, the fusion of s-indacene with two pyrene moieties lead to IDPs with absorption maxima approaching the near infrared (NIR) regime.

Master's Thesis is focused on production of CO2 from fossil fuels combustion and the methods of CO2 emission from fossil fuels combustion reduction, resp. pre-combustion and post-combustion separation of CO2. Recapitulation of world consumption of primary energetic resources and carbon dioxide production as a result of theirs combustion in years 1971 - 2006 was made using a number of information sources. Whilst combustion o fossil fuel is related with production of CO2, calculation of emission rate of CO2 from fossil fuels (natural gas, crude oil and coal) was demonstrated. The Case Study of energy and material balances of gas turbine cycle with synthesis of methane from CO2 and from hydrogen which is produced in water splitting was made, using CHEMCAD software.

Dans ce cadre de cette thèse, nous nous intéressons à la conception, à la synthèse et à la caractérisation des propriétés physicochimiques de dérivés lipophiles d’extractibles du bois. Nous avons ainsi envisagé de modifier la structure de trois flavonoïdes dont la ressource est importante à partir de différentes essences de bois : la catéchine, le mesquitol et la naringénine pour incorporer des fonctionnalités supplémentaires. Les applications visées ici concernent principalement la protection des matériaux, en l’occurrence le bois et les métaux corrodables. En ce qui concerne la préservation du bois, il semble possible d’envisager différentes stratégies pour inhiber l’action de dégradation des champignons sur le bois. L’imprégnation des composés antioxydant tels que les polyphénols dans le bois, seuls ou en association avec un biocide pour agir en synergie, permet de limiter les effets des radicaux ou autres oxydants utilisés et générés par les pourritures, L’objectif de la modification structurale est ici d’augmenter leur hydrophobie pour limiter leur lessivage en cas d’utilisation du matériau en conditions extérieures. La deuxième application visée est la protection des matériaux métalliques. En effet, l’utilisation des produits antioxydants naturels comme inhibiteur de corrosion permet de substituer les inhibiteurs inorganiques ou les molécules organiques d’origine pétrochimique (polyamines, Imidazole…), car leur production est coûteuse et elles sont issues de ressources non renouvelables. Le greffage d’une chaîne hydrocarbonée hydrophobe sur des polyphénols ayant des propriétés antioxydantes permet d’obtenir un film protecteur sur le matériau / Within the framework of this thesis, we are interested in the design, synthesis and characterization of the physicochemical properties of lipophilic derivatives of wood extractives. We have thus considered modifying the structure of three flavonoids whose resource is important from different wood species: catechin, mesquitol and naringenin to incorporate additional functionalities. The applications reported here mainly deal with the protection of materials like wood and corrodible metals. With respect to wood preservation, it seems possible to consider different strategies to inhibit the wood degradation related to fungi on wood. Impregnation of antioxidant compounds such as lipophilic polyphenols on wood can limit the effects of radicals or other oxidants used and generated by rots. The second intended application is the protection of metallic materials. Indeed, the use of natural antioxidants as a corrosion inhibitor replace inorganic inhibitors or organic molecules (polyamines, imidazole...), because their production is expensive and toxic. The grafting of a hydrophobic hydrocarbon chain on polyphenols which have antioxidant properties allows the formation of protective films on the material

In dieser Arbeit wurde die Rolle der L-Aminosäureoxidase IL4I1 für die Progression von Glioblastomen analysiert. IL4I1 wird in diesem Hirntumor erhöht exprimiert und führt dadurch zu einem Abbau der drei aromatischen Aminosäuren Tryptophan (Trp), Phenylalanin und Tyrosin zu ihren entsprechenden α-Ketosäuren (Pyruvaten). In-vitro-Versuche mit IL4I1-überexprimierenden Glioblastomzelllinien zeigen, dass nur das aus Trp-gebildete Indol-3-pyruvat (I3P) bzw. dessen nachgeschaltete Abbauprodukte eine Aktivierung des Arylhydrocarbon Rezeptors (AHR) und seiner Signaltransduktion in Glioblastomen bewirkt. Des Weiteren wurde der Einfluss von IL4I1 in der Tumor-Mikroumgebung auf die Kompetenz von T-Zellen charakterisiert. Das von den Tumorzellen gebildete und sezernierte I3P vermittelt eine Aktivierung des AHR in beiden T-Zellsubpopulationen. Damit einhergehend werden zwei Mechanismen ausgelöst, die die Tumorprogression fördern: eine Proliferationsinhibierung CD8+ zytotoxischer T-Zellen und eine vermehrte Differenzierung immunsuppressiver Treg.

oundry production, which forms an integral part of the engineering industry, is a source of waste with a negative impact on the working and living environment. The pressure on greening the production in all production branches of industry does not dodge the foundry industry and technical engineers seek out possibilities of decreasing the negative impact of the production of casting on the environment. An important source of environmentally dangerous waste in foundry operation is the use of organic compounds during the preparation of shaping and core mixtures. Their substitution with materials that would ensure similar technological features of the shaping and core mixtures as the organic materials used hitherto and at the same time decrease the amount of solid, liquid and gaseous ecologically undesirable compounds used in or arising during the preparation and use of shaping and core mixtures, would be significant for decreasing the ecological burden connected to casting production. A promising group of materials usable as components of shaping and core mixtures are the biopolymer materials which can substitute the organic connective systems used in the production of foundry cores by the means of the so-called hot processes – Hot-Box and Warm-Box. This work focuses on the exploration of the technological and ecological features of several biopolymer materials available on the domestic market which have the potential to become a full alternative of the binders used so far on the basis of urea-formaldehyde, melamine-formaldehyde, phenol-formaldehyde and furan resins.

In the reservoir conditions, a petroleum fluid is defined by its thermodynamic and volumetric properties and by its physicochemical properties. Their behaviors are modeled from experimental data in order to properly simulate the processing of these fluids during the production.   With the advent of new regulations and rigidity that exist at the custom regulations today, research centers have great difficulty in obtaining large amounts of samples. For these reason, although there are several methods to characterize the different components of crude oil, the laboratories are turning increasingly to techniques that requires lower amounts of samples: micro-distillation, gas chromatography (GC).   The micro-distillation is a fast and completely computerized technique made to substitute the standard distillation for analysis of liquid petroleum products. Advantages of the method compared to the standard distillation are the reduction of working time by at least a factor of 4, the small sample volumes required for distillation (few micro liters). [24]   This report is aimed to create a simple model that can predict yield curves of physical distillation, without using the micro-distillation technique. The results obtained through gas chromatography (GC) analysis by laboratory technicians enable the modeling of the fluid behavior. Having identified and treated practically all aspects of micro-distillation through simulations with PRO/II, I found out that, regardless of the setting and the thermodynamic method used, there are always significant differences between simulation results and those of the micro-distillation.   The result shows that it’s still difficult to create a model which can replace micro-distillation and gas chromatography (GC) because of the huge gap between the simulation results and micro-distillation. Furthermore, the dynamics revealed that the micro distillation is not accurate. I had hoped to get additional results by studies the correlations with more samples, but that did not turn out to be the case. Regardless of that, I think that it would be interesting to study more samples and use another simulator to properly represent micro distillation. This could be an interesting topic for further studies. / Under de föhållanden som reservoarens miljö erbjuder, definieras en petroleumvätska av dess termodynamiska och volymetriska egenskaper och av dess fysikalisk-kemiska egenskaper. För att korrekt simulera bearbetningen av dessa vätskor under produktion, deras beteende modelleras från experimentella data Med tillkomsten av nya regler och oflexibilitet som finns på tullbestämmelser vid gränserna idag, har forskningscenter stora svårigheter att få större mängder prover levererade. Av den anledningen, trots att det finns flera metoder för att karakterisera de olika komponenterna av råolja, tvingas laboratorier att vända sig mer och mer till alternativa analysmetoder som kräver mindre provvolymer: mikrodestillation, gaskromatografi, etc.   Mikrodestillation, som är en snabb och helt datoriserad teknik, visar sig kunna ersätta standarddestillation för analys av flytande petroleumprodukter. Fördelar med metoden jämfört med standarddestillering är minskad arbetstidsåtgång med minst en faktor 4. Därtill krävs endast en begränsad provvolym (några mikroliter) i jämförelse med standarddestillation.  [24]   Denna rapport syftar till att skapa en enkel modell som kan förutsäga avkastningskurvan av fysisk destillation, utan att använda mikrodestillationsteknik. De resultat som erhölls genom gaskromatografiska analyser möjliggjorde modelleringen av det vätskebeteendet hos det analyserade provet. Efter att ha identifierat och behandlat praktiskt taget alla viktiga aspekter av mikro destillation genom simuleringar med PRO/II, fann jag att, oberoende av inställningen och den termodynamiska metod som används,  det alltid finns stora skillnader mellan simulering och mikro destillation.   Resultatet visar att det fortfarande är svårt att skapa en modell som kan ersätta mikrodestillering och gaskromatografi på grund av differensen mellan simuleringsresultaten å ena sidan, och resultaten från mikrodestillering å andra sidan. Dessutom visade resultaten att mikrodestillation som analysmetod inte ger tillförlitliga resultat. Min förhoppning var att få ytterligare användbara resultat genom att studerar potentiella korrelationer emellan fler prover, men detta visade sig inte vara fallet. Jag anser att det skulle vara intressant att studera fler prover och använda en annan simulator för att bättre representera mikrodestillation. Detta skulle kunna vara ett intressant ämne för vidare studier.