19 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2695" Qinhua Huang. 12/19/2004. Report is also available in paper and microfiche from NTIS.

La mise au point de nouvelles méthodes de synthèse flexibles, robustes et polyvalentes pour la formation régiosélective de liaisons carbone-carbone ou carbone-hétéroatome représente un défi perpétuel en chimie organique. Dans le cadre de nos travaux, nous avons développé des protocoles efficaces et faciles à mettre en œuvre portant sur l’activation de liaisons C-O catalysée par le nickel et la sulfénylation de liaisons C-H sans métal. Nous avons démontré que l’utilisation d’un système catalytique simple à base d’acétate de nickel(II) et d’oxyde de triphénylphosphine dans des conditions douces (40 °C) permettait de réaliser le couplage croisé entre un éther d’énol méthylique et un réactif de Grignard via l’insertion du Ni dans la liaison C OMe. Une réaction de sulfénylation électrophile de composés (hétéro)aromatiques a également été développée. L’emploi de N-thiosuccinimides comme partenaires soufrés, en présence d’acide trifluoroacétique, nous a permis de réaliser avec une très bonne régiosélectivité la sulfénylation d’aromatiques électro-enrichis. Cette méthode a également été appliquée à des indoles non protégés afin d’accéder à des 2-thioindoles fonctionnalisés. / The development of new flexible synthetic methods for the regioselective formation of carbon carbon or carbon-heteroatom represents an ongoing challenge in organic chemistry. The work presented in this manuscript concerns the development of efficient and easy to implement protocols on nickel-catalyzed C-O bond activation and metal-free C-H sulfenylation.It was demonstrated that the use of a single catalytic system based on nickel(II) acetate and triphenylphosphine oxide under mild conditions (40 ° C) could perform the cross-coupling between an alkenyl methyl ether and a Grignard reagent via the insertion of the Ni catalyst into the C-OMe bond. An electrophilic sulfenylation reaction of (hetero)aromatics has also been developed. The use of N thiosuccinimides as sulfenylating partners, in the presence of trifluoroacetic acid, allowed us to achieve with a very good regioselectivity the sulfenylation of electron-rich aromatics. This method was also applied to unprotected indoles in order to access functionalized 2 thioindoles.

In the current agriculture is essential to adopt management strategies, low environmental impact. In this context, the environment comprising plant roots is of utmost importance, since they are in constant contact with microorganisms such as growth promoting rhizobacteria (RPCPs), known to affect the metabolism and resistance of plants, may help them dealing with biotic and abiotic stresses via promotion of growth, induced resistance, production of phytohormones compounds, volatile organic compounds (VOCs) and ability to fix nitrogen. Studies of associative rhizobacteria led to discovery of Azospirillum genus isolated in grasses and cereals grown in several countries of tropical and temperate. Regarding endophytic microorganisms G. diazotrophicus is a Gram-negative bacteria, obligatory aerobic and non-spore forming isolated initially from sugar cane in Brazil. This study was based on the assumption that the RPCPs can change the resistance of plants to insect herbivores, and to evaluate the influence of the joint action of two strains of RPCPs (Gluconacetobacter diazotrophicus and Azospirillum sp) in metabolome of plant cane -Sugar variety SP 79-1011 but also in plant defense mechanism herbivory by Diatraea saccharalis. The metabolites present in higher concentration both in inoculated plants as on control plants were identified by analysis metaolomica by the NMR technique. Compounds identified in higher concentration in inoculated plants were carbohydrates, aromatic compounds, amino acids and organic acids. In control plants and amino compounds were inetrmediarios Krebs cycle. Changes in the volatile organic compounds VOCs profile were identified by gas chromatography coupled to mass spectrometry. Qualitative and quantitative changes have occurred in the overall volatile profile emitted by plants inoculated as compared to the profile of volatile issued by the control plants, which could be contributing to preference Diatraea saccharalis the control plants from the plants inoculated in bioassay chance choice. VOCs present changes in the profile of infested plants with Diatraea saccharalis. Bioassay no choice there was no significant difference in saccharalis Diatraea weight gain fed control or inoculated plants. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Na agricultura atual é essencial a adoção de estratégias de manejo, de baixo impacto ambiental. Nesse contexto o ambiente que engloba as raízes das plantas é de extrema importância, uma vez que ela está em constante contato com microrganismos tais como rizobactérias promotoras do crescimento (RPCPs), conhecidos por afetar o metabolismo e a resistência das plantas, podendo ajuda-las a lidar com estresses bióticos e abióticos via promoção de crescimento, resistência induzida, produção de compostos fitohormonios, compostos orgânicos voláteis (COVs) e capacidade de fixar nitrogênio. Estudos com as rizobactérias associativas levaram a descoberta do gênero Azospirillum, isolado em gramíneas forrageiras e cereais cultivados em diversos países de clima tropical e temperado. Em relação aos microrganismos endofíticos G. diazotrophicus é uma bactéria Gram-negativa, aeróbica obrigatória e não-formadora de esporos isolada inicialmente a partir de cana-de-açúcar no Brasil. O presente estudo foi embasado na hipótese de que as RPCPs podem alterar a resistência de plantas a insetos herbívoros, tendo como objetivo avaliar a influencia da ação conjunta de duas estirpes de RPCPs (Gluconacetobacter diazotrophicus e Azospirillum sp) no metaboloma de plantas de cana-de-açúcar da variedade SP 79-1011 como também nos mecanismo de defesa da planta a herbivoria por Diatraea saccharalis. Os metabólitos presentes em maior concentração tanto em plantas inoculadas quanto em plantas do controle foram identificados por análise metaolômica pela técnica de RMN. Os compostos identificados em maior concentração nas plantas inoculadas foram carboidratos, compostos aromáticos, aminoácidos e ácidos orgânicos. Nas plantas do controle os compostos foram aminoácido e inetrmediários do ciclo de Krebs. Alterações no perfil de compostos orgânicos voláteis COVs foram identificados por cromatografia gasosa acoplada a espectrometria de massas. Alterações qualitativas e quantitativas ocorreram no perfil geral de voláteis emitidos pelas plantas inoculadas quando comparado ao perfil de voláteis emitido pelas plantas do controle, fato que poderia estar contribuindo para preferência de Diatraea saccharalis pelas plantas do controle em relação as plantas inoculadas no bioensaio com chance de escolha. Ocorreu alteração no perfil de COVs de plantas infestadas com Diatraea saccharalis. No bioensaio sem chance de escolha não se observou diferença significativa no ganho de peso de Diatraea saccharalis alimentadas com plantas do controle ou inoculadas.

Made available in DSpace on 2014-12-17T14:08:52Z (GMT). No. of bitstreams: 1 RaoniBA_DISSERT.pdf: 2283831 bytes, checksum: 9e3bfc1213fc5b5ac439fb175ddc5631 (MD5) Previous issue date: 2012-12-14 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The retail fuel stations are partially or potentially polluters and generators of environmental accidents, potentially causing contamination of underground and surface water bodies, soil and air. Leaks in fuel retail stations? underground storage systems are often detected in Brazil and around the world. Monoaromatic hydrocarbons, BTEX (benzene, toluene, ethylbenzene and xylenes) and polycyclic aromatic hydrocarbons (PAHs) are an indication of the presence of contamination due to its high toxicity. This paper presents a case study of contamination in a Fuel Retail Station by petroleum derivative products in the city of Natal. For identification and quantification of the hydrocarbons, EPA analytical methods were used. The values of benzene quantified by EPA method 8021b CG-PID/FID, ranged from 1.164 to 4.503 mg.Kg-1 in soil samples, and from 12.10 to 27,639 μg.L-1 in underground water samples. Among the PAHs, naphthalene and anthracene showed the most significant results in soil samples, 0.420 to 15.46 mg.Kg-1 and 0.110 to 0,970 mg.Kg-1, respectively. In underground water samples, the results for Naphthalene varied between 0.759 and 614.7 μg.L-1. PAHs were quantified by EPA Method 8270 for GCMS. All of the results for the chemical analysis were compared with the values for the CONAMA 420/2009 resolution. The results for benzene (27,639 μg.L-1) showed levels highly above the recommended by the CONAMA 420 resolution, wherein the maximum permissible for underground water is 5 μg.L-1. This is a worrying factor, since underground water makes up 70% of the city of Natal?s water supply / The retail fuel stations are partially or potentially polluters and generators of environmental accidents, potentially causing contamination of underground and surface water bodies, soil and air. Leaks in fuel retail stations? underground storage systems are often detected in Brazil and around the world. Monoaromatic hydrocarbons, BTEX (benzene, toluene, ethylbenzene and xylenes) and polycyclic aromatic hydrocarbons (PAHs) are an indication of the presence of contamination due to its high toxicity. This paper presents a case study of contamination in a Fuel Retail Station by petroleum derivative products in the city of Natal. For identification and quantification of the hydrocarbons, EPA analytical methods were used. The values of benzene quantified by EPA method 8021b CG-PID/FID, ranged from 1.164 to 4.503 mg.Kg-1 in soil samples, and from 12.10 to 27,639 μg.L-1 in underground water samples. Among the PAHs, naphthalene and anthracene showed the most significant results in soil samples, 0.420 to 15.46 mg.Kg-1 and 0.110 to 0,970 mg.Kg-1, respectively. In underground water samples, the results for Naphthalene varied between 0.759 and 614.7 μg.L-1. PAHs were quantified by EPA Method 8270 for GCMS. All of the results for the chemical analysis were compared with the values for the CONAMA 420/2009 resolution. The results for benzene (27,639 μg.L-1) showed levels highly above the recommended by the CONAMA 420 resolution, wherein the maximum permissible for underground water is 5 μg.L-1. This is a worrying factor, since underground water makes up 70% of the city of Natal?s water supply

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-21T15:41:03Z No. of bitstreams: 0 / Made available in DSpace on 2016-12-21T15:41:03Z (GMT). No. of bitstreams: 0 / Compostos fenólicos vêm despertando preocupação nos últimos anos e incitando grande atenção em todo o mundo ao desenvolvimento de métodos de determinação e monitoramento contínuo no ambiente devido a sua elevada toxicidade e persistência no meio ambiente, principalmente no sedimento, que devido sua característica em acumular compostos faz desse um dos compartimentos mais importantes na avaliação do nível de contaminação de ecossistemas aquáticos continentais. Neste estudo foi desenvolvido um método analítico utilizando cromatografia a gás acoplada ao detector de espectrometria de massas (GC/MS) para a determinação de seis compostos fenólicos e foi avaliada a presença dos mesmos em amostras de sedimento do Reservatório Guarapiranga, um reservatório de usos múltiplos da água, destinado principalmente para abastecimento público de água potável da Região Metropolitana de São Paulo. Para garantir a reprodutibilidade do método de forma confiável atendendo aos objetivos e qualidade propostos, a metodologia desenvolvida foi submetida ao processo de validação, em que os parâmetros seletividade, linearidade, faixa de trabalho, limite de detecção, limite de quantificação, tendência/recuperação, precisão (repetitividade, precisão intermediária e reprodutibilidade) e robustez foram avaliados. A metodologia aqui proposta mostrou ser adequada para alcançar o objetivo de avaliar os compostos em estudo, e pela sua aplicação foi constatada a presença dos compostos fenol e 3-metilfenol no sedimento do reservatório. Nas amostras de sedimento coletadas em 2011, o fenol foi o composto encontrado com maior frequência, com alguns resultados acima do LQ, principalmente em pontos com maior influência urbana, em concentrações de 0,09 a 0,19 μg g-1. Também foi encontrado o 3-metilfenol com resultados acima do LQ em dois pontos de coleta, G-11 e G-13, nas concentrações de 0,10 e 0,19 μg g-1 respectivamente. Já na coleta realizada em outubro de 2014, o composto 3-metilfenol foi quantificado em dois pontos de coleta, G-02 e G-07, nas concentrações de 0,07 e 0,08 μg g-1 respectivamente, sendo detectado abaixo do LQ em diversos pontos ao longo do reservatório. A presença destes compostos mesmo em baixas concentrações pode indicar uma contaminação decorrente de atividades industriais nas margens do reservatório e considerando-se que os compostos em sedimento com o tempo podem ser liberados na coluna dágua e causar contaminação na água de abastecimento este estudo fornece subsídios para revisão da legislação vigente que não estabelece limites para os compostos fenólicos na matriz de estudo. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Le sujet de cette thèse se situe dans le cadre général des arylations de nucléophiles catalysées par des complexes de métaux de transitions (Cu, Fe) ou réalisées en absence de ces derniers, dans des conditions compétitives et respectueuses de l’environnement. Ces réactions sont d’une importance majeure pour l’industrie chimique. Dans un premier chapitre est tout d’abord décrit un couplage inédit mettant en jeu un sel d’aryldiazonium et un nucléophile azoté (formation de liaison CAr-N). La méthode procède dans des conditions douces via un système catalytique au cuivre peu coûteux et peu toxique. Les produits de couplage obtenus (Ar-NHet) sont d’un intérêt central dans l’industrie pharmaceutique et agrochimique. Dans une deuxième partie nous avons présenté une méthode permettant de réaliser le couplage entre des sels d’aryldiazonium et des dérivés du styrène, à l’aide d’un système t BuOK/DMF. Cette réaction, réalisée pour la première fois en absence de catalyseurs à base de métaux de transition, permet d’accéder, via la formation de liaisons CArsp²-Csp², à des motifs stilbènes variés qui trouvent de nombreuses applications en chimie pharmaceutique. Un deuxième chapitre porte sur l’utilisation de dérivés de l’iode hypervalent permettant la fonctionnalisation de noyaux aromatiques (C-H) ou de dérivés vinyliques (C-H). Une première méthode décrit une réaction de triflimidation directe de composés acétanilides avec une sélectivité exclusive en position para. Deux conditions réactionnelles ont été mises en place pour cette fonctionnalisation. Une première utilise une quantité stœchiométrique de PhI(OAc)2 et une autre utilise une quantité catalytique d’iodotoluène (génération in-situ de l’iode(III)). Cette transformation a conduit à la formation de liaisons CAr-N en présence de bis(trifluorométhane)sulfonimide de lithium (LINTf2) comme nucléophile azoté. Dans une deuxième partie, nous avons montré que l’iodure de bisphosphoranilidène (PNPI), pouvait catalyser la trifluorométhylation vinylique sélective de dérivés du styrène en présence d’un réactif de l’iode hypervalent (l’iode(III)), le réactif de Togni II. Des travaux sont en cours pour tenter de comprendre l’influence positive de l’utilisation de PNPI dans le cas de notre réaction. Un troisième chapitre décrit des résultats préliminaires permettant d’obtenir un rendement honorable (54%) lors du couplage catalysé au fer du 4-iodotoluène avec le phényllithium. Une autre série de test décrit le couplage entre des halogénures d’aryle et des alkyllithium primaires. La méthode semble très efficace, puisque par ailleurs les travaux très récents de la littérature pour des couplages similaires faisant intervenir les mêmes partenaires réactionnels, font appel à des catalyseurs de fer ou de palladium. / This thesis is part of a very general search seek to develop methodologies for environmentally sustainable conversion of small molecules into more valuable substances catalyzed by copper and iron complexes or under metal-free conditions. The work focuses on the functionalization of aromatic rings by C-C or C-N bond formation.In a first chapter, a novel coupling involving an aryldiazonium salt and a nitrogenous nucleophile (CAr-N bond formation) is first described. The method proceeds under mild conditions using a cheap and non-toxic copper catalyst system. The obtained coupling products (Ar-NHet) are of central interest in the pharmaceutical and agrochemical industry. Then in a second part, a method allowing the coupling between aryldiazonium salts and styrene derivatives, using a BuOK / DMF system is presented. This reaction, carried out for the first time in the absence of catalysts based on transition metals, makes it possible to access to various stilbene units which find numerous applications in pharmaceutical chemistry.A second chapter concerns the use of hypervalent iodine derivatives allowing the functionalization of aromatic or vinyl substrates. A first method describes a direct triflimidation reaction of acetanilide compounds with an exclusive selectivity in the para position. Two reactions conditions have been established for this functionalization. One uses a stoichiometric amount of PhI(OAc)2 and another uses a catalytic amount of iodotoluene (in-situ generation of iodine (III)). This transformation resulted in the formation of CAr-N bonds in the presence of lithium bis (trifluoromethane) sulfonimide (LINTf2) as the nitrogen nucleophile. In a second part, we have shown that bisphosphoranilidene iodide (PNPI) can catalyze a selective vinylic trifluoromethylation of styrene derivatives in the presence of a hypervalent iodine reagent (iodine (III)), Togni’s reagent II. Work is under way to try to understand the positive influence of PNPI.A third chapter describes preliminary results of an iron-catalyzed heterocoupling of 4-iodotoluene an phenylithium system allowing the obtention of an honorable yield (54%) during the coupling of 4-iodotoluene with phenyllithium. Another series of tests describes the coupling between aryl halides and primary alkyllithiums. The method seems to be very effective, since very recent work in the literature for similar couplings involving the same reaction partners involves catalysts of iron or palladium.

[pt] A alta viscosidade dos óleos pesados e o elevado teor de asfaltenos contribuem para a formação de emulsões água-em-óleo (A/O) altamente estáveis, dificultando a separação óleo/água e aumentando os custos de produção e transporte. Para reduzir a viscosidade, técnicas de diluição são comuns com solventes simples. Portanto, pouca pesquisa foi realizada sobre o impacto dos compostos aromáticos nas propriedades interfaciais e na estabilidade das emulsões, de solventes complexos, como o querosene. Neste estudo, investigou-se o efeito da segregação dos compostos aromáticos do querosene nas propriedades bulk e interfaciais e na estabilidade dos asfaltenos e das emulsões A/O. Além disso, foram analisadas as correlações desses efeitos com a desemulsificação química. Inicialmente, foram avaliadas as propriedades interfaciais de frações de surfactantes naturais, extraídas de um óleo pesado brasileiro, em relação à sua capacidade de estabilizar emulsões água-querosene. Os resultados indicaram que a estabilidade dessas emulsões decorre do efeito sinérgico entre as resinas e os asfaltenos, resultando na formação de filmes interfaciais mais flexíveis, que evitam ou retardam a coalescência das gotas. Entretanto, quando o querosene foi utilizado como diluente do óleo pesado (HO) na fase oleosa, observou-se a floculação e precipitação dos asfaltenos. Esses resultados foram correlacionados com a composição química de dois tipos de querosene: um composto apenas por saturados (KeS) e outro contendo 30 por cento massa de compostos aromáticos (KeSA). Verificou-se que a composição química dos querosenes afeta a estabilidade coloidal dos asfaltenos, a estabilidade da emulsão e as propriedades interfaciais. KeSA apresentou maior solubilização e dispersão dos asfaltenos em comparação ao KeS. Além disso, a viscoelasticidade interfacial diminuiu quando o teor de querosene foi maior ou igual a 30 por cento massa, indicando a formação de filmes interfaciais menos rígidos. Porém, o módulo de elasticidade nos sistemas contendo KeSA aumentou gradualmente com o tempo, sugerindo uma melhor solubilidade dos asfaltenos e uma adsorção controlada pela difusão facilitada na interface. A concentração de aromáticos do solvente (KeSA) mantém a estabilidade do filme interfacial durante a diluição de HO, compensando assim a perda de asfaltenos com o aumento do teor de querosene na fase óleo. Os resultados também destacaram o papel crucial da aromaticidade do querosene na quebra das emulsões A/O contendo 20 por cento massa de Ke na fase oleosa. Diferentes desemulsificantes químicos, comumente utilizados como bases para desemulsificantes comerciais, bem como compostos modelo, foram testados. KeSA apresentou maior robustez e resistência à quebra das emulsões. Esse efeito decorre da segregação interfacial dos compostos aromáticos do querosene. Esses resultados enfatizam a importância da composição química do querosene quando é usado na diluição de óleos pesados, o qual tem efeito significativo na estabilidade e quebra das emulsões A/O. / [en] The high viscosity of heavy oils and the high content of asphaltenes contribute to the formation of highly stable water-in-heavy oil (W/O) emulsions, making oil/water separation difficult and increasing production and transportation costs. To reduce viscosity, dilution techniques with simple solvents are common. Therefore, slight research has been conducted on the impact of aromatic compounds on interfacial properties and emulsion stability from complex solvents, such as kerosene. In this study, we investigated the effect of segregation of aromatic compounds in kerosene on the bulk and interfacial properties and stability of asphaltenes and W/O emulsions. Furthermore, we analyzed the correlations of these effects with chemical demulsification. Initially, we evaluated the interfacial properties of natural surfactants fractions extracted from Brazilian heavy oil regarding their ability to stabilize water-kerosene emulsions. The results indicated that the stability of these emulsions was related to the synergistic effect between resins and asphaltenes, resulting in the formation of more flexible interfacial films that prevent or delay the coalescence of the droplets. However, when kerosene was used as diluent of heavy oil (HO) in the oil phase, flocculation and precipitation of asphaltenes were observed. These results were correlated with the chemical composition of two kerosene types: one composed only of saturates (KeS) and another containing saturates and 30 percent wt. of aromatic compounds (KeSA). It was found that the chemical composition of the kerosene affects the colloidal asphaltenes stability, emulsion stability, and interfacial properties. KeSA showed greater solubilization and dispersion of asphaltenes compared to KeS. Additionally, interfacial viscoelasticity decreased when the kerosene content was bigger or equal 30 wt. percent, indicating the formation of less rigid interfacial films. However, the interfacial elastic modulus in systems containing KeSA gradually increased over time, suggesting better solubility of asphaltenes and diffusion-controlled adsorption at the interface. The concentration of solvent aromatics (KeSA) maintains interfacial film stability during HO dilution, thus compensating for the loss of asphaltenes with increasing kerosene content in the oil phase. The results also revealed the crucial role of kerosene s aromaticity in the breaking of W/O emulsions containing 20 wt. percent of kerosene in the oil phase. Various chemical demulsifiers commonly used as bases for commercial demulsifiers, as well as model compounds, were tested. The presence of KeSA exhibited greater robustness and resistance to emulsion breaking. This effect was attributed to interfacial segregation of aromatic compounds from kerosene. These results emphasize the importance of kerosene s chemical composition when used for diluting heavy oils, as it has a significant effect on the stability and breaking of W/O emulsions, particularly in the case of the Brazilian heavy oil used in this study.

L'étude de l'oxydation d'hydrocarbures naphténiques (éthyl-cyclohexane, n-butyl-cyclohexane) et aromatiques (éthyl-benzène, n-butyl-benzène, n-hexyl-benzène) a été réalisée en réacteur auto-agité par jets-gazeux (pression de 1 à10 bar, température de500 à1100 K, richesse : 0,25, 1 et 2, temps de passage:2s). Les produits de réaction ont été quantifiés par chromatographie en phase gazeuse et identifiés par couplage avec la spectrométrie de masse. L'influence sur la réactivité et sur la sélectivité de la richesse, de la pression et de la taille de la chaîne alkyle greffée sur le cycle aromatique ou naphténique a été déterminée. La réactivité de l'éthyl-cyclohexane a également été comparée à celle obtenue pour deux autres composés contenant 8 atomes de carbone (le n-octane et le 1-octène). Les résultats expérimentaux pour l'éthyl-cyclohexane et le n-butyl-benzène sont en bon accord avec des prédictions réalisées à l'aide de modèles de la littérature, sauf pour le composé naphténique pour des températures inférieures à 800 K. Un mécanisme cinétique détaillé d'oxydation de l'éthyl-benzène a été développé (1411 réactions ; 205 espèces) et validé à partir des résultats obtenus lors de cette thèse mais également à partir de résultats disponibles dans la littérature. Ce mécanisme constitue la « base aromatique » implémentée dans le nouveau logiciel EXGAS Alkyl-aromatiques développé parallèlement à cette thèse et qui permet la génération automatique de mécanismes cinétiques d'oxydation des composés Alkyl-aromatiques. Une étude des règles génériques de décomposition des espèces primaires dans le mécanisme secondaire de ce logiciel a été réalisée lors de cette thèse / The study of the oxidation of naphthenic (ethyl-cyclohexane,n-butyl-cyclohexane) and aromatic (ethyl-benzene,n-butyl-benzene, n-hexyl-benzene) hydrocarbons was performed in a jet-stirred reactor (pressure from 1 to10 bar, temperature from 500 to 1100 K, equivalenceratio: 0.25, 1 and2, residence time: 2s). Reaction products were quantified by gas chromatography and identified using mass spectrometry. The influence on the reactivity and the product selectivity of the equivalence ratio, the pressure and the size of the side alkyl chain attached tothe aromatic or naphthenic ringwas determined. The reactivity of ethyl-cyclohexane was also compared to that obtained for two other compounds containing 8 carbon atoms (n-octane and1-octene). The experimental results for ethyl-cyclohexane and n-butyl-benzene have been satisfactorily compared with prediction made using detailed kinetic mechanisms from the literature, except for the naphthenic at temperature below 800 K. A detailed kinetic mechanismfor the oxidation of ethyl-benzene has been developed (1411 reactions, 205 species) and validated from experimental results obtained in this studybut also from results available in literature. This mechanism has now becomethe "aromatic base" implemented in the software EXGAS Alkyl-aromaticswhich has been developed together with this PhD work and which allows theautomatic generation of alkyl-aromatics oxidation kinetic mechanisms. A study of the generic rules of decomposition of primary species in the secondary mechanism of this softwarewas conducted in this thesis

Syftet med denna rapport var att utreda hur föroreningsmängder och föroreningskoncentrationer i dagvattendammars sediment påverkas av markanvändningen i avrinningsområdet. Sedimentprovtagning skedde under april 2019 i tre dagvattendammar i Gävle, med olika markanvändningar: industri, villaområde samt två avrinningsområden innehållande trafik. Markanvändningen ”trafik vid Västerbacken” hade en trafikintensitet på cirka 2000 bilar/dygn och ”trafik vid Hamnleden” en intensitet på 7000 bilar/dygn. Provtagningen utfördes med rysskannborr och sedimentdjup mättes för att kvantifiera sedimentvolymen i dagvattendammarna. Proverna skickades till laboratorie för analys av metaller, fosfor, alifater, aromater samt polycykliska aromatiska kolväten [PAH]. Dagvattendammen med markanvändning industriområde hade sedimentet med högst föroreningskoncentrationer, följt av villaområde – trafik vid Hamnleden – trafik vid Västerbacken. Resultaten för denna studie visar att inga markanta skillnader kan ses vid jämförelse av föroreningskoncentrationer i sedimentet, utifrån omgivande markanvändning. Markanvändningarna visade liknande koncentrationsmönster i de grafiska figurer som jämfördes. Resultatet kan bero på att dagvattendammarna ligger geografiskt nära och därmed kan bli påverkade av samma atmosfäriska nedfall och bakgrundshalter. Det förväntades inte att föroreningskoncentrationerna i villaområdets sediment skulle vara näst högst. En förklaring kan vara den högre halten organiskt material i villaområdets sediment, vissa föroreningar tenderar att binda starkt till organiskt material. Däremot sågs stora skillnader mellan dagvattendammarnas föroreningsmängder i sedimentet (jämförelsetalet ”fastlagd förorening per år”), vilket återspeglades av sedimentvolymen. Störst mängd föroreningar och störst sedimentvolym sågs i dagvattendammen med markanvändning industriområde. I fallande skala följde trafik vid Hamnleden – trafik vid Västerbacken – villaområde. Resultatet kan bero på skillnader i andel partikulära fraktioner i dagvattnet från respektive markanvändning, där industriområdet i så fall har störst andel partikulära fraktioner enligt resultatet i denna studie. Beräkningar utfördes i StormTac för teoretisk föroreningstransport i inkommande dagvatten till dagvattendammarna. Beräkningarna genererade i totalmängder (lösta och partikulära fraktioner). När föroreningstransporten jämfördes med ”fastlagd förorening per år” för villaområde sågs att föroreningstransportens mängder var markant större, vilket delvis kan förklaras med att totalmängder jämfördes med partikulära mängder. En slutsats som dras är att omgivande markanvändning påverkar föroreningsmängderna i sedimentet och sedimentvolymen, snarare än koncentrationerna. / This thesis addresses how human activities in the catchment area could influence the contaminant concentrations and amounts of contaminants in the sediments of stormwater ponds. Sediment sampling was done in April 2019. The storm water ponds had different land uses: industrial, residential (detached area) and two land uses of traffic with different intensities; “traffic by Hamnleden” (7000 cars/day) and “traffic by Västerbacken” (2000 cars/day). Samples were taken with a Russian corer and sediment depth was measured to quantify sediment volume. Samples were sent to laboratory for analysis of metals, phosphorus, aliphatics, aromatics and polycyclic aromatic hydrocarbons [PAH]. The stormwater pond with industry as land use had the highest concentration of contaminants in the sediment, followed by residential area – traffic by Hamnleden – traffic by Västerbacken. The results of this study showed that the land use concentrations of contaminants were all similar, and the patterns of concentration in the graphic figures were similar. The results could be explained by the narrow geographic area in which the three storm water ponds are situated. They could be affected by the same atmospheric downfall which could even out the concentrations. It was not expected that the residential area would have one of the highest concentrations in the sediment. This could be explained by the high content of organic matter, as some contaminants create strong chemical bonding with organic matter. Bigger differences were seen for the amounts of contaminants in the sediments and the comparative figure “fixated amount of contaminant per year”. The land use industry had the highest amount of contaminants followed by traffic by Hamnleden – traffic by Västerbacken – residential area. This is probably due to differences in particle quota in the storm water coming from the land uses. Calculations were done for the amount of transported contaminants in stormwater, via the watershed management tool and model StormTac. The calculated transportation of contaminants resulted in total amounts of contaminants, meaning both dissolved and particulate fractions. The calculations from StormTac were compared with the comparative figure “fixated amount of contaminant per year” for the land use residential area, and the amounts were significantly higher for the calculated transportation. This could partly be explained by comparing total amounts with particulate amounts. A conclusion of this report is that land use affects the amounts of contaminants and sediment volume in the studied storm water ponds, rather than the concentrations.

La simulación molecular presenta la ventaja de ofrecer un marco teórico importante para predecir propiedades termodinámicas y de transporte de fluidos con aplicaciones industriales. En este trabajo, se explotó está ventaja para predecir el equilibrio líquido vapor de agua, compuestos aromáticos y sus mezclas a condiciones tanto sub- como supercríticas. Se realizó una comparación de diferentes potenciales intermoleculares conocidos mediante el cálculo de propiedades termodinámicas de sistemas puros que sirvió de punto de partida para llevar a cabo una optimización de parámetros transferibles para un potencial intermolecular de agua y compuestos aromáticos. En el caso de agua, se llevo a cabo el análisis y evaluación de propiedades termodinámicas de un modelo simple de agua. En este modelo, las contribuciones electrostáticas se aproximan mediante interacciones de corto alcance en vez de las típicas fuerzas de Coulomb de largo alcance. En general, se han encontrado grandes desviaciones con respecto a los datos experimentales, tal como un valor de temperatura crítica de 360K, valor 50% alejado del valor experimental. Debido a que estos resultados nos indican la importancia de incluir las fuerzas de Coulomb en el modelo molecular empleado para reproducir correctamente las propiedades de agua, el trabajo de investigación se ha enfocado en la optimización de los parámetros de los potenciales TIP4P y SPC/E. Los resultados obtenidos muestran que es posible encontrar una mejor aproximación al punto crítico experimental a partir de la optimización del modelo SPC/E. Sin embargo, el buen acuerdo con los experimentos del modelo original a condiciones ambiente se pierde usando los parámetros del modelo optimizado. Por otro lado, la estimación de propiedades de compuestos aromáticos esta de acuerdo con los datos experimentales permitiendo la reproducción de la densidad de líquido saturado, presión de saturación y entalpía de vaporización para compuestos puros. Finalmente, en el caso de mezclas se ha aplicado el conjunto de parámetros obtenidos para aromáticos. Las propiedades termodinámicas de la mezcla binaria aromático-aromático y aromático agua son analizadas en un amplio rango de temperaturas y presiones. Las desviaciones encontradas entre los valores calculados y los experimentales sugieren aplicar un mejor método de optimización para sistemas puros o por otro lado, promover un potencial de interacción intermolecular más sofisticado. Las estimaciones a condiciones cercanas al punto crítico están en buen acuerdo con los datos experimentales. / La simulació molecular presenta l'avantatge d'oferir un marc teòric important per a cercar propietats termodinàmiques i de transport de fluids amb aplicacions industrials. En aquest treball es va explotar aquesta avantatge per predir l'equilibri líquid vapor d'aigua, components aromàtics i les seves mescles, tant a condicions sub com supercrítiques. Es va realitzar una comparació de diferents potencials intermoleculars, coneguts mitjançant el càlcul de propietats termodinàmiques de sistemes purs, que ha servit de punt de sortida per portar a terme una optimització de paràmetres transferibles per a un potencial intermolecular de propietats termodinàmiques d'un model simple d'aigua. En aquest model, les contribucions electrostàtiques s'aproximen mitjançant interaccions de curt abast en lloc de les típiques forces de Coulomb de llarg abast. En general, s'ha trobat grans desviacions respecte a les dades experimentals, tal com un valor de temperatura crítica de 360K, valor 50% allunyat del valor experimental. Degut a que aquests resultats ens indiquen la importància d'incloure les forces de Coulomb en el model molecular emprat per reproduir correctament les propietats d'aigua, el treball d'investigació s'ha enfocat en l'optimització dels paràmetres dels potencials TIP4P i SPC/E. Els resultats obtinguts mostren que és possible trobar una millor aproximació al punt crític experimental a partir de l'optimització del model SPC/E. No obstant, el bon acord amb els experiments del model original a condicions ambientals es perden usant els paràmetres del model optimitzat. Per altre banda, l'estimació de propietats de compostos aromàtics esta d'acord amb les dades experimentals permetent la reproducció de la densitat de líquid saturat, pressió de saturació i entalpia de vaporització per a compostos purs mitjançant el potencial AUA-Aromátics proposat. Finalment, en el cas de mescles s'ha aplicat el conjunt de paràmetres obtinguts per aromàtics. Les propietats termodinàmiques de la mescla binària aromàtic-aromàtic i aromàtic-aigua són analitzades en un ample rang de temperatures i pressions. Les desviacions trobades entre els valors calculats i els experimentals suggereixen aplicar un millor mètode d'optimització per a sistemes purs o, per altre banda, promoure un potencial d'interacció intermolecular més sofisticat. Les estimacions en condicions properes al punt crític tenen un bon acord amb les dades experimentals. / Molecular simulation presents the advantage of providing a unified theoretical framework to model fluid properties for industrial applications. In this work we exploit this advantage to predict thermodynamic properties of pure water and aromatics and their mixtures at sub- and supercritical conditions. A comprehensive comparison of different intermolecular potentials has been carried out in order to analyze model predictions for pure component properties. In addition, an optimization of transferable parameters has been performed for an intermolecular potential for aromatics and water. In the case of water, an analysis and evaluation of the thermodynamic properties of a simple model has been performed. In this model, the electrostatic contributions are approximated by short-range interactions instead of the typical long-range Coulombic forces. On the whole, we found huge deviations with experimental data, such as a critical temperature value of 360K, 50% far away from the experimental value. Since, these calculations indicate the importance of including the electrostatic contribution in order to correctly model water, we also focus on reproducing critical properties from an optimization of the well known TIP4P and SPC/E water model parameters. Results obtained show that a better approximation to the critical point prediction is possible from the optimization of the SPC/E parameters, however, the good agreement with experiments for the original model at room conditions vanishes using the optimized parameters. On the other hand, thermodynamic property estimations of aromatic molecules are in good agreement with experimental data and we are able to reproduce saturation liquid densities, saturation pressures, vaporization enthalpies and liquid structure for pure compounds. Finally, in the case of mixtures, we applied the optimized set of parameters obtained for aromatics. The thermodynamic properties of binary aromatic-aromatic and aromatic water mixtures are analyzed over a wide range of temperatures and pressures. Deviations between the predicted and experimental values are found at low temperatures and high densities suggesting that a better optimization process needs to be performed for the pure systems or a more sophisticated intermolecular interaction potential is needed. Nevertheless, the estimations close to critical conditions are in good agreement with experimental data.