<p dir="ltr">As people in the U.S. spend 90% of their time indoors, their exposure to indoor air pollutants released during the use of household consumer products cannot be overlooked. Studies have shown that consumer products such as disinfectants, cleaning agents, and personal care products (PCPs) contain complex mixtures of volatile organic compounds (VOCs). Monoterpenes, added as active ingredients in cleaning agents and fragrances, are commonly detected in these products. Monoterpenes can react with ozone (O₃) and initiate the formation of secondary organic aerosol (SOA). Siloxanes, another category of compounds commonly found in PCPs, can bioaccumulate and may adversely impact the environment and human health.</p><p><br></p><p dir="ltr">Most prior studies have evaluated chemical emissions from these products using offline techniques, such as sorbent tube sampling followed by gas chromatography-mass spectrometry (GC-MS). Few studies have been conducted during real-life use of these products in indoor environments. Considering that many indoor activities are often transient, the composition of indoor air can be rapidly altered. Real-time monitoring of indoor VOCs and aerosols is necessary to capture the temporal variations in emissions during indoor activities and to evaluate their impact on indoor air chemistry, human exposure, and outdoor air quality. In addition, O₃also plays an important role in indoor chemistry. Indoor O₃concentrations are strongly linked to ventilation system operation and occupancy patterns, as the ventilation from outdoors is the major source of indoor O₃ and occupants are a major sink of indoor O₃. However, studies on how ventilation modes and occupancy impact spatiotemporal distributions of indoor O₃are limited.</p><p><br></p><p dir="ltr">Hazardous chemical incidents can potentially be another unexpected source of indoor pollutants, releasing volatile chemicals which can be transported to indoor environments via building ventilation. Evaluation of air, water, and soil contamination and human exposure risks is critical in the emergency response to hazardous chemical incidents, to develop effective remediation strategies. An effective and reliable approach to assess air, water, and soil contamination, and subsequent human exposures, is urgently needed.</p><p dir="ltr">To fill these research gaps, this dissertation aims to: (1.) characterize gas- and particle-phase emissions in real-time during common indoor activities, including surface disinfection, cleaning, and hair styling; (2.) evaluate the impact of indoor emissions on human health and the atmospheric environment; (3.) map the spatiotemporal distribution of O₃ and CO₂ concentrations throughout a building ventilation system; (4.) develop a methodology for rapid screening of VOCs in surface water samples collected from a chemical disaster site.</p><p><br></p><p dir="ltr">To achieve research goals (1.) and (2.), a field campaign was conducted at the Indiana University Research and Teaching Preserve (IURTP) field laboratory in summer 2019 and two field campaigns were conducted at the Purdue zero Energy Design Guidance for Engineers (zEDGE) Tiny House in fall 2020 and summer 2021 to characterize emissions from the use of cleaning agents, disinfectants, and hair care products in indoor environments, respectively. A proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) was used to monitor the mixing ratios of VOCs in real-time. To achieve research goal (3.), a multi-point sampling system was created at the Herrick Living Laboratories and its ventilation system in spring and summer 2019 to monitor spatiotemporal trends in O₃concentrations. To achieve goal (4.), a controlled static headspace sampling system, in conjunction with a high-resolution PTR-TOF-MS was developed to analyze surface water samples collected from East Palestine, Ohio, U.S. in the weeks after a train derailment and subsequent chemical spill and burn.</p>

Tradicionalmente los programas de mejora del melocotón (Prunus persica (L.) Batsch) se centraron fundamentalmente en la obtención de genotipos elite de alta productividad, resistentes a plagas y patógenos, adaptados a diferentes zonas agroecológicas y que produzcan frutos de gran tamaño y buen aspecto. Como resultado, muchos de estos programas han obtenido cultivares de excelentes características agronómicas. No obstante, el mejoramiento selectivo hacia caracteres agronómicos puede ir en detrimento de la calidad organoléptica del fruto como fue demostrado en el caso de fresa y tomate donde algunos aromas se perdieron en el proceso de mejora (Klee and Giovannoni, 2011; Olbricht et al., 2008). En melocotón, la disminución de la calidad del fruto ha sido percibida por los consumidores y además es la mayor causa de insatisfacción de los mismos (Bruhn et al., 1991). Un probable consecuencia de esto puede ser el bajo consumo de melocotón en comparación con otras frutas como el plátano y la manzana (Crisosto, 2006). Estudios pioneros han establecido que el aroma es uno de los atributos principales por los cuales los consumidores juzgan la calidad del melocotón (Bruhn, 1995). El aroma está definido íntegramente por los compuestos volátiles orgánicos (VOCs) los cuales también contribuyen al sabor del fruto en combinación con azucares y ácidos orgánicos. Los volátiles del melocotón han sido estudiados con anterioridad, describiéndose un poco más de 100 compuestos incluyendo: lactonas, esteres, terpenos, aldehídos, ácidos carboxílicos y alcoholes entre otros [(Aubert and Milhet, 2007) y referencias incluidas]. La identificación de regiones génicas y genes candidatos para el control de los aromas del fruto resulta un punto fundamental para su posterior implementación en programas de mejora con el fin de obtener melocotones de mayor calidad. En este sentido nos propusimos la identificación de QTLs (del inglés ``Quantitative trait loci'') y genes candidatos involucrados en la producción de los compuestos volátiles del melocotón. El desarrollo reciente de un conjunto técnicas analíticas de mayor potencia permitió el advenimiento de una nueva plataforma tecnológica, la metabolómica, que contempla el análisis global de los metabolitos de un organismo permitiendo abordar la evaluación de calidad de una forma más exhaustiva. Dentro de ellas, la tecnología HS-SPME-GC-MS (del inglés ``Head Space-Solid Phase Microextraction-Gas Chromatography-Mass Spectroscopy'') es actualmente el método de elección para el análisis de volátiles debido a su alta sensibilidad, reproducibilidad y robustez (Tikunov et al., 2005). Además el análisis en conjunto de los datos derivados de la metabolómica con otras tecnologías de alto rendimiento para el análisis de expresión de genes, como lo son los microarrays, ha permitido el descubrimiento de genes implicados la producción de diversos metabolitos en Arabidopsis y tomate (Mounet et al., 2009; Saito and Matsuda, 2010; Carrera et al. 2012). En una primera instancia nos propusimos el desarrollo de una plataforma de alto rendimiento basada en HS-SPME-GC-MS para la identificación y cuantificación de compuestos volátiles en fruto de melocotón. Se ensayarán diferentes protocolos para la extracción de los compuestos volátiles con el fin de identificar el más adecuado (es decir el más sensible manteniendo la reproducibilidad y con una robustez satisfactoria). Una vez desarrollado un protocolo adecuado se analizará en paralelo la evolución de los compuestos volátiles y la expresión de genes mediante microarrays durante la maduración de diferentes genotipos de melocotón con el objetivo de identificar patrones comunes de co-regulación entre metabolitos y genes durante el desarrollo del fruto. Por último, se propuso la identificación de regiones génicas implicadas en la producción de volátiles mediante análisis de QTLs. / Sánchez, G. (2013). Cartografiado de QTL y genes candidatos asociados a metabolitos determinantes de la calidad de fruto en melocotón [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/34511

Orientador: Edson Tomaz / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-10T00:00:54Z (GMT). No. of bitstreams: 1 Albuquerque_EdlerLinsde_D.pdf: 18576988 bytes, checksum: f5a08b5bbd306ca352ba5e96455e69d8 (MD5) Previous issue date: 2007 / Resumo: Realizou-se um estudo experimental dos Compostos Orgânicos Voláteis (COV) encontrados na atmosfera urbana da Região Metropolitana de São Paulo (RMSP). O objetivo principal foi medir as concentrações de COV, procurando identificar, por meio de análises multivariadas, relações entre estas concentrações, parâmetros meteorológicos e concentrações de outros poluentes. Métodos de amostragem passiva e ativa foram empregados utilizando tubos de aço contendo o sólido adsorvente TENAX TA. A quantificação das amostras ocorreu por dessorção térmica automática e cromatografia gasosa com detecção por ionização em chama. Analisou-se COV selecionados, incluindo alcanos, cicloalcanos e compostos aromáticos. Diversos aspectos foram investigados em estudos específicos: emissão veicular, variabilidade diária das concentrações, emprego da amostragem passiva, potencial para formar ozônio etc. As concentrações registradas em cada campanha variaram bastante em função de aspectos associados a características locais das fontes de emissão, horários de coleta, fatores sazonais e meteorológicos. Verificou-se que tolueno, m,p-xilenos, n-hexano, etilbenzeno e 1,2,4-trimetilbenzeno foram os COV encontrados em maiores concentrações na maioria dos estudos realizados, estando os mesmos entre os mais emitidos pelos veículos e entre aqueles com maior potencial para formar ozônio. No local monitorado, o perfil de variação temporal das concentrações de COV foi diferente em função de condições sazonais e/ou meteorológicas. A validação da amostragem passiva possibilitou estimar taxas de amostragem dos COV, as primeiras da literatura científica para vários compostos e as primeiras obtidas numa atmosfera urbana de cidades brasileiras. Isto viabilizou a realização de um monitoramento passivo simultâneo em oito locais diferentes, permitindo verificar as vantagens deste tipo de coleta. Acredita-se que os resultados desta pesquisa possam auxiliar na criação de planos de monitoramento para os COV / Abstract: The aim of this research was an experimental study of Volatile Organic Compounds (VOCs) found in the urban atmosphere of Metropolitan Area of São Paulo (MASP). The main purpose was to measure atmospheric concentrations of VOCs. Multivariate analyses were used to identify relationships among VOCs concentration, meteorological parameters and concentrations of other pollutants. Passive and active sampling methods were applied. Steel tubes packed with adsorbent TENAX TA were employed. The samples were quantified by automatic thermal desorption and gas chromatography with flame ionization detection. Selected VOCs were analyzed, including alkanes, cycloalkanes and aromatic compounds. Many topics related to VOCs were investigated: vehicular emissions, time variation of concentrations, employ of passive sampling, potential of ozone formation etc. For this, some specific studies were conducted. VOCs concentration vary a lot in each campaign in function of aspects associated to local characteristics of emission sources, sampling time, season and meteorological factors. In most of performed studies toluene, m,p-xylenes, n-hexane, ethylbenzene and 1,2,4-trimethylbenzene were VOCs found in higher concentrations. Additionally, such compounds were also found among VOCs with higher vehicular emission factors and higher ozone forming potentials. At the monitoring site, VOCs concentrations have shown distinct profile of time variation for different seasonal and meteorological conditions. VOCs uptake rates were estimated from the validation of passive sampling process. These uptake rates were the first found for many VOCs and the first found in an urban atmosphere of Brazilian cities. This fact became possible to perform a simultaneous passive monitorization campaign in eight different sites at MASP, verifying the advantages of this type of sampling strategy. It is believed that the results of this research may aid in the creation of monitoring programs for VOCs / Doutorado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Le méconium constitue les premières selles du nourrisson. Cette matrice complexe est analysée dans le cadre du projet « PENEW » (Pregnancy Environment and NEWborn malformations) afin de déterminer si le degré d'exposition fœtale aux xénobiotiques joue un rôle dans la survenue de malformations congénitales. Le but de cette étude était le développement analytique pour la détection et la quantification dans le méconium d’une quarantaine de composés de familles différentes (composés organiques volatils, pesticides, éthers de glycol et les métabolites associés). Trois techniques analytiques différentes et une préparation d’échantillon spécifiques ont été développées pour la détection et la quantification de ces composés dans le méconium. L’application des ces méthodes à 246 échantillons de méconium a montré une exposition fœtale à plusieurs des substances recherchées. / Meconium is the earliest stool of newborns. This complex matrix was analyzed through the "PENEW" project (Pregnancy and Newborn malformations Environment) to determine if the degree of fetal exposure to xenobiotics has an influence in the occurrence of birth defects. The objective of this thesis was developed analytical methods for the detection and quantification of several different families of compounds (volatile organic compounds, pesticides, glycol ethers and their metabolites) in meconium. Three different analytical methods and a specific sample preparation have been developed for the detection and quantification of these compounds in the meconium. The application of these methods to 246 meconium samples showed a fetal exposure to several target compounds.

La biosurveillance humaine consiste en des mesures de produits chimiques ou de leurs métabolites dans des liquides biologiques. Ces données biologiques sont souvent interprétées en les comparant à des valeurs dites bio-équivalentes aux valeurs toxicologiques de référence (VTR) qui ont été pour la plupart définies grâce à l’utilisation de modèles animaux dans un contexte de simple exposition chimique. Pourtant, elles peuvent résulter de co-expositions multivoies (cas des composés organiques volatils (COVs)) pouvant donner lieu à des interactions toxicocinétiques chez humain. Des approches de modélisation toxicocinétique à base physiologique (TCBP) ont été conçues pour étudier ces interactions. Mais, leur impact sur la variabilité interindividuelle (VI) de la toxicocinétique des substances individuelles, et l’évaluation résultante du risque toxique des contaminants chimiques suite à une exposition multivoies, n’ont que peu ou pas été investigués. Par ailleurs, des études proposent une approche de reconstitution directe de l’exposition chimique externe à partir de mesures sanguines de COVs (composés parents) grâce à des modèles TCBP probabilistes, souvent construits pour des adultes de 70 kg, et des calculs de probabilité. C’est la dosimétrie inverse. Mais les incertitudes associées aux estimations d’exposition externe faites grâce à cette approche à partir de mesures biologiques ponctuelles collectées lors des enquêtes de santé n’ont presque pas été étudiées. La présente recherche doctorale vise à caractériser l’impact des co-expositions chimiques multivoies sur la variabilité interindividuelle de la toxicocinétique des COVs, en vue d’en tenir éventuellement compte dans la mise au point dans cette thèse d’approches appliquées de dosimétrie inverse. Dans un premier temps, nous avons construit des modèles TCBP multivoies pour deux mélanges (benzène, toluène, éthylbenzène et m-xylène (BTEX) d’une part, et trichloroéthylène et chlorure de vinyle (TCE-CV) d’autre part) pour des sous-populations humaines d’âges différents (y compris une sous-population d’adultes). Ces modèles ont été couplés à des simulations de Monte Carlo pour explorer l’impact des co-expositions multivoies sur la VI de la toxicocinétique des substances individuelles en cas d’expositions ‘’faibles’’ ou ‘’élevées’’. Des index de variabilité (IV) ont été calculés comme étant le rapport du 95 ème centile de la distribution d’une dose interne chez les autres sous-populations étudiées au 50 ème centile de la même distribution chez les adultes. Dans un deuxième temps, nous avons raffiné l’approche existante de dosimétrie inverse en développant des modèles TCBP probabilistes d’inhalation pour des sous-populations canadiennes (d’âge, de poids corporel et de taille différents) dont les mesures sanguines de toluène ont été collectées lors du cycle 3 de l’enquête canadienne sur les mesures de la santé (ECMS-3), en vue de reconstituer leur exposition externe correspondante. Enfin, nous avons développé une approche individuelle de dosimétrie inverse pour estimer l’exposition externe au toluène à partir des mesures urinaires d’un de ses métabolites (l’acide S-benzylmercapturique, ou en anglais : S-benzylmercapturic acid ou BMA) rapportées chez des individus Canadiens. Ici, deux techniques ont été testées pour cette estimation : estimer l’exposition au toluène à partir des mesures ponctuelles de BMA urinaire d’une journée complète obtenues chez chaque individu et estimer l’exposition à partir d’une mesure individuelle de BMA urinaire sur des urines de 24 h. L’approche individuelle nous a permis de proposer une méthode pour quantifier l’incertitude, c’est-à-dire l’erreur possible, sur les estimations d’exposition externe faites par dosimétrie inverse à partir des mesures ponctuelles provenant des enquêtes de santé. Cette étude doctorale a révélé que l’impact des co-expositions multivoies sur la VI toxicocinétique peut dépendre des composés des mélanges et du niveau d’exposition à ces substances. Par exemple, la variation obtenue sur les IVs basés sur la quantité de substance métabolisée par les CYP2E1 est d’environ -9 à -5 % et -38 à -33% pour le benzène respectivement pour les expositions ‘’faibles’’ et ‘’élevées’’ simulées au mélange. Pour le CV et le TCE, elle est respectivement de -17 à -13% et -20 à -11% pour les expositions ‘’élevées’’, et nulle pour les ‘’faibles’’ expositions au mélange. Les expositions au toluène dans l’air estimées par dosimétrie inverse dans cette thèse (médianes entre 0,004 et 0,01 ppm) sont bien en dessous des valeurs guides maximales recommandées par Santé Canada pour une exposition chronique et suggèrent une exposition via l’air intérieur. L’incertitude mentionnée plus haut, quant à elle, varie entre 15 et 23 % dans le cadre de nos travaux. La présente étude doctorale a contribué à améliorer l’évaluation du risque toxicologique des COVs. / Human biomonitoring consists in the measurements of chemicals or their metabolites in biological matrices. These biological data are often interpreted by comparison with so-called bio-equivalent values to the toxicological reference values (TRV) which have for the most part been defined through the use of animal models in a context of simple chemical exposure. However, biomonitoring data can result from multi-routes co-exposures to multiple chemical such as Volatile Organic Compounds (VOCs), which can give rise to toxicokinetic interactions in the human body. Physiologically-based pharmacokinetic (PBPK) modeling approaches have been developed to study these interactions. But, their impact on the interindividual variability (IV) of the toxicokinetics of individual substances, and the evaluation of the toxic risk of chemical contaminants, that may result from multi-routes exposure, have only been sparsely studied. Further, the scientific literature suggests an approach for the direct reconstruction of external chemical exposure from blood measurements of VOCs’ parent compounds. This is generally done for 70-kg adults by the use of appropriate PBPK models, combined with a probability calculation approach, in a process called “reverse dosimetry”. But the uncertainties associated with estimates of external exposure made using this approach from biological spot measurements collected during health surveys have hardly been studied. The current doctoral research aims to characterize the impact of multi-routes chemical co-exposures on the interindividual variability of toxicokinetics, in order to account it for in the development in this thesis of applied approaches of reverse dosimetry. First, we built multi-routes probabilistic PBPK models for two mixtures (benzene, toluene, ethylbenzene and m-xylene (BTEX) on one hand, and trichloroethylene and vinyl chloride (TCE-VC) on the other hand) for human subpopulations of different ages (including one of adults). These models were coupled with Monte Carlo simulations in order to explore the impact of multi-routes co-exposures on the IV of the toxicokinetics of individual compounds at ‘low’ or ‘high’ exposures. Variability indices (VIs) were calculated as the ratio of the 95th percentile value of the distribution of an internal dose in the other subpopulations studied to the 50th percentile value of the same distribution in adults. In a second step, we refined the existing reverse dosimetry approach by developing probabilistic inhalation PBPK models for Canadian subpopulations (of different age, body weight and size) whose blood toluene measurements were collected during the third cycle of Canadian Health Measures Survey (CHMS-3), in order to reconstruct their corresponding external exposure. Finally, we have developed an individual reverse dosimetry approach to estimate external exposure to toluene from urinary measurements of one of its metabolites (S-benzylmercapturic acid or BMA) reported in Canadian individuals. Two techniques were tested here for this estimation: estimating toluene exposure from spot measurements of urinary BMA of a full day obtained in each individual and estimating exposure from an individual measurement of urinary BMA performed on 24-h urines. The individual approach allowed us to propose a method to quantify the uncertainty, that means the possible error, on the estimates of external exposure made by reverse dosimetry from spot measurements from health surveys. This doctoral study revealed that the impact of multi-routes co-exposures on IV of toxicokinetics may depend on the compounds in the mixtures and the level of exposure to these substances. For example, the variation obtained on the amount of substance metabolized by CYP2E1-based VIs based is about -9 to -5% and -38 to -33% for benzene respectively for 'low' and 'high' exposures simulated to the mixture. For VC and TCE, it is respectively about -17 to -13% and -20 to -11% for "high" exposures, and zero for "low" exposures to the mixture. The exposures to toluene in air estimated by reverse dosimetry in this thesis (median between 0.004 and 0.01 ppm) are well below the maximum guideline values recommended by Health Canada for chronic exposure and suggest an exposure of Canadian studied via indoor air. The uncertainty mentioned above varies between 15 and 23% in the context of our work. The present doctoral study has contributed to improving the assessment of the toxicological risk of VOCs.

Die kürzliche globale COVID-19-Pandemie hat deutlich gezeigt, dass hohe medizinische Kosten eine große Herausforderung für unser Gesundheitssystem darstellen. Daher besteht eine wachsende Nachfrage nach personalisierten tragbaren Geräten zur kontinuierlichen Überwachung des Gesundheitszustands von Menschen durch nicht-invasive Erfassung physiologischer Signale. Diese Dissertation fasst die Forschung zur Laserkarbonisierung als Werkzeug für die Synthese flexibler Gassensoren zusammen und präsentiert die Arbeit in vier Teilen. Der erste Teil stellt ein integriertes zweistufiges Verfahren zur Herstellung von laserstrukturiertem (Stickstoff-dotiertem) Kohlenstoff (LP-NC) ausgehend von molekularen Vorstufen vor. Der zweite Teil demonstriert die Herstellung eines flexiblen Sensors für die Kohlendioxid Erfassung basierend auf der Laserumwandlung einer Adenin-basierten Primärtinte. Die unidirektionale Energieeinwirkung kombiniert mit der tiefenabhängigen Abschwächung des Laserstrahls ergibt eine neuartige geschichtete Sensorheterostruktur mit porösen Transducer- und aktiven Sensorschichten. Dieser auf molekularen Vorläufern basierende Laserkarbonisierungsprozess ermöglicht eine selektive Modifikation der Eigenschaften von gedruckten Kohlenstoffmaterialien. Im dritten Teil wird gezeigt, dass die Imprägnierung von LP-NC mit Molybdäncarbid Nanopartikeln die Ladungsträgerdichte verändert, was wiederum die Empfindlichkeit von LP-NC gegenüber gasförmigen Analyten erhöht. Der letzte Teil erläutert, dass die Leitfähigkeit und die Oberflächeneigenschaften von LP-NC verändert werden können, indem der Originaltinte unterschiedliche Konzentrationen von Zinknitrat zugesetzt werden, um die selektiven Elemente des Sensormaterials zu verändern. Basierend auf diesen Faktoren zeigte die hergestellte LP-NC-basierte Sensorplattform in dieser Studie eine hohe Empfindlichkeit und Selektivität für verschiedene flüchtige organische Verbindungen. / The recent global COVID-19 pandemic clearly displayed that the high costs of medical care on top of an aging population bring great challenges to our health systems. As a result, the demand for personalized wearable devices to continuously monitor the health status of individuals by non-invasive detection of physiological signals, thereby providing sufficient information for health monitoring and even preliminary medical diagnosis, is growing. This dissertation summarizes my research on laser-carbonization as a tool for the synthesis of functional materials for flexible gas sensors. The whole work is divided into four parts. The first part presents an integrated two-step approach starting from molecular precursor to prepare laser-patterned (nitrogen-doped) carbon (LP-NC). The second part shows the fabrication of a flexible LP-NC sensor architecture for room-temperature sensing of carbon dioxide via laser conversion of an adenine-based primary ink. By the unidirectional energy impact in conjunction with depth-dependent attenuation of the laser beam, a novel layered sensor heterostructure with a porous transducer and an active sensor layer is formed. This molecular precursor-based laser carbonization method enables the modification of printed carbon materials. In the third part, it is shown that impregnation of LP-NC with molybdenum carbide nanoparticle alters the charge carrier density, which, in turn, increases the sensitivity of LP-NC towards gaseous analytes. The last part explains that the electrical conductivity and surface properties of LP-NC can be modified by adding different concentrations of zinc nitrate into the primary ink to add selectivity elements to the sensor materials. Based on these factors, the LP-NC-based sensor platforms prepared in this study exhibited high sensitivity and selectivity for different volatile organic compounds.

L’oxydation photocatalytique des Composés Organiques Volatils (COVs) apparaît comme un procédé très prometteur pour la réduction de la pollution atmosphérique. Ce travail avait pour objectif d’étudier l’oxydation photocatalytique de plusieurs COVs au sein d’un réacteur annulaire: méthyléthylcétone (MEK), acétone, 1-propanol ou encore triéthylamine (TEA). Dans une première partie, l’influence de plusieurs paramètres cinétiques tels que la concentration en polluant, l’intensité lumineuse, le temps de contact et le taux d’humidité a été étudiée. Un mécanisme de dégradation photocatalytique a été établi pour chaque polluant en fonction des sous-produits détectés par GC/MS. Dans une seconde partie, la diffusion de radicaux hydroxyles OH• dans la phase gazeuse, après activation photonique du TiO2, a été mise en évidence par Fluorescence Induite par Laser (LIF). Pour la première fois, ces radicaux OH• ont été détectés à des pressions proches des conditions atmosphériques. Dans ce cas, nous pouvons en conclure que la dégradation photocatalytique des COVs pourrait être partiellement due à une réaction en phase gazeuse entre les COVs et les radicaux OH• / Photocatalytic oxidation of airborne contaminants appears to be a promising process for remediation of air polluted by Volatile Organic Compounds (VOCs). The aim of our study is the photocatalytic oxidation of several VOCs using an annular reactor: methylethylketone (MEK), acetone, 1-propanol and triethylamine (TEA). First, the influence of different kinetic parameters such as pollutant concentration, incident light irradiance, contact time and humidity has been studied. A mechanistic pathway has been indeed proposed for each pollutant according to the produced intermediates species detected by GC/MS. Second, the diffusion of hydroxyls radicals OH• in gas phase, after photonic activation of TiO2, has been highlighted using Laser-Induced Fluorescence (LIF). For the first time, OH• radicals have been detected at atmospheric pressures, close to the major photocatalytic oxidation conditions, leading to the assumption that the photocatalytic degradation of VOCs might be at least partially occurs between pollutants and OH• radicals in gas-phase

Volatile Organic Compounds (VOCs) are one of the main groups of odour causing compounds in Waste Water Treatment Plants (WWTP). Adsorption technology is already established, in recent years the interest for the optimization of the costs associated with this technique has grown significantly. In particular, there are different options, from the use of low cost adsorbents, to reducing costs associated with carbon regeneration process. In this thesis, the adsorption of the three VOCs on sewage sludge based adsorbents was studied. It was proved that adsorbents obtained by chemical activation of sewage sludge with alkaline hydroxides are comparable to commercial activated carbons (ACs). Likewise, the adsorption of multicomponent gaseous streams was also studied. Related to the ACs regeneration, it was proposed a regeneration treatment of VOC saturated ACs with H2O2 based on advanced oxidation processes (AOP). The influence of the surface chemistry of ACs in this regeneration process was also studied. / Los compuestos orgánicos volátiles (COVs) son unos de los principales compuestos causantes de olores en las emisiones de EDARs. La adsorción es una técnica ampliamente utilizada para la eliminación de COVs en corrientes gaseosas y en los últimos tiempos ha crecido significativamente el interés para la optimización de los costes relacionados con esta técnica. En esta tesis se estudió el proceso de adsorción tres COVs en adsorbentes preparados a partir de lodos de EDAR, comprobando que adsorbentes obtenidos mediante activación química de lodos de depuradora son comparables a carbones activados comerciales (CAs). También se estudió la adsorción de corrientes multicomponente de COVs. En referencia a la regeneración del carbón activado, se propuso un tratamiento de regeneración con H2O2 de CAs saturados con COVs basado en los procesos avanzados de oxidación. Asimismo se estudió la influencia de la química superficial de los CAs en el proceso de regeneración con H2O2.

Made available in DSpace on 2015-05-14T13:00:13Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2275378 bytes, checksum: fcb4196c739d83997818dc074daf738f (MD5) Previous issue date: 2010-03-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The pharmacological effects of carvacrol, a monoterpenoid phenol, on the cardiovascular system were studied in normotensive rats, using in vivo and in vitro techniques. In superior mesenteric artery rings isolated from rats with functional endothelium carvacrol (10-8 - 3 ₓ 10-4 M) concentration-dependently relaxed phenylephrine-induced contractions (pD2 = 4.59  0.02, MR = 103.03  1.5%, N=8) and this effect was not altered after removal of the endothelium (pD2 = 4.36  0.02, MR = 111.03  4.8%, N=8), suggesting that the vasorelaxant response induced by carvacrol appears to be independent of vascular endothelium. Furthermore, carvacrol antagonized the vasoconstriction induced by high K+ solution (Tyrode with 80 mM of KCl) (pD2 = 4.12  0.01, MR = 94.38  3.97%, N=6), inhibited contraction elicited by CaCl2 in depolarizing (KCL 60 mM) nominally without Ca2+ medium out carvacrol also antagonized the contractions induced by the L-type Ca2+ channel agonist, S(-)-Bay K 8644 (pD2 = 4.537  0.023, MR = 9.8  3.58%, N=6), indicating that the vasodilatation involve probably the inhibition of Ca2+ influx through L-type voltage-dependent calcium channels (Cav type-L). Additionally, carvacrol antagonized the contractions induced by CaCl2 in nominally without Ca2+ medium in the presence of PHE and nifedipine, suggesting a possible inhibition of calcium influx by store operated channels (SOC), receptor operated channels (ROC) and/or TRP channels. Interestingly, in a depolarizing (KCL 60 mM) nominally without Ca2+ medium and in the presence of nifedipine, carvacrol also inhibited the contraction induced by CaCl2, suggesting a probable inhibition of SOC and/or TRP channels. To evaluate the involvement of TRP channels in the vasorelaxant effect induced by carvacrol, non-selective inhibitors were used. No change in the relaxation response was observed in the presence of ruthenium red (pD2= 4.31  0.029, N=6), however, the effect induced by carvacrol was potentiated by La3+ (pD2 = 5.231  0,04, N=6), Gd3+ (pD2 = 4.97  0.02, N=6) or Ni2+ (pD2 = 5.079  0.02, N=6), furthermore, Mg2+ (pD2 = 4.168  0.021; MR = 81.12  4.03%, N=6) attenuated the relaxation elicited by carvacrol, suggesting that monoterpenoid may to action on TRPC1, TRPC3, TRPC6 and TRPM7 channels. Carvacrol also induced hypotension and bradycardia in non-anesthetized normotensive rats. In conclusion, these results suggest that carvacrol induced vasorelaxant effect in superior mesenteric artery rats isolated probably inhibiting Ca2+ influx by Cav, SOC (TRPC1), ROC (TRPC1 or TRPC6) and TRPM7 channels. Moreover, the effects induced by carvacrol in normotensive non-anesthetized rats showed a hypotensive and bradycardic activity. / Os efeitos farmacológicos de carvacrol, um fenol monoterpenóide, sobre o sistema cardiovascular, foi estudado em ratos normotensos, usando técnicas in vivo e in vitro. Carvacrol (10-8 - 3 ₓ 10-4 M) induziu vasorelaxamento dos anéis de artéria mesentérica superior isolada de rato pré-contraídos com 10 μM FEN (pD2 = 4,59  0,02, Emáx = 103,03  1,5%) na presença do endotélio funcional e esse efeito não foi alterado após a remoção do endotélio (pD2 = 4,36  0,02, Emáx = 111,03  4,8%), sugerindo, portanto, que a resposta vasorelaxante induzida por carvacrol parece ser independente do endotélio vascular. Interessantemente em anéis pré-contraídos com KCl 80 mM (pD2 = 4,12  0,01, Emáx = 94,38  3,97%), observou-se uma diminuição na sua potência e na sua eficácia farmacológica, sugerindo um passo comum na via que seria um aumento citosólico dos níveis de cálcio. Adicionalmente, carvacrol antagonizou, de maneira dependente de concentração, as contrações induzidas por CaCl2 em meio despolarizante nominalmente sem Ca2+ e induziu relaxamento das contrações induzidas pelo S(-)-Bay K 8644 (pD2 = 4,537  0,023, Emáx = 91,8  3,58%) com uma diminuição na sua eficácia farmacológica, sugerindo uma inibição do influxo de cálcio por canais de Ca2+ tipo-L. Além disso, antagonizou as contrações induzidas por CaCl2 em meio nominalmente sem cálcio, na presença de FEN e nifedipina, sugerindo uma provável inibição do influxo de cálcio por SOC, ROC e/ou canais TRP. Como também, em um meio despolarizante e nominalmente sem cálcio na presença de nifedipina esse mesmo antagonismo foi observado, ressaltando a provável inibição dos SOC e/ou canais TRP. Para avaliar a participação dos canais TRP, as preparações foram incubadas com La3+ (pD2 = 5,231  0,04) , Gd3+ (pD2 = 4,97  0,02) e Ni2+ (pD2 = 5,079  0,02) onde seu efeito foi potencializado sugerindo sua ação sobre os canais TRPC e ao utilizar magnésio (pD2 = 4,168  0,021 e Emáx = 81,12  4,03%) tanto sua potência quanto sua eficácia farmacológica foi atenuada, sugerindo inibição do canal TRPM7. Nos estudos in vivo, em ratos normotensos não anestesiados, carvacrol produziu hipotensão e bradicardia. Em conclusão, esses resultados sugerem que carvacrol induz efeito vasorelaxante em anéis de artéria mesentérica superior isolada de rato por inibir provavelmente TRPM7, como também inibir o influxo de cálcio por Cav, SOC, ROC e ou TRPC1 e 6. Além disso, os efeitos induzidos por carvacrol em ratos normotensos não anestesiados mostrou uma atividade hipotensora e bradicárdica.

Les pompiers méditerranéens sont confrontés à des embrasements soudains de la végétation (AFF) dont les mécanismes ne sont pas encore bien compris. La végétation étant l'unique combustible, nous nous sommes penchés sur les gaz qui en proviennent. Nous avons d’abord étudié la dégradation thermique de quatre Composés Organiques Volatils biogéniques (COVb) à l'aide d'une pyrolyse flash et d'un four tubulaire. À partir de cette étude et de la littérature, nous avons choisi un mélange d'étude afin expérimenter ses propriétés de combustion. Nous avons ainsi déterminé l'Énergie Minimale d’Inflammation (EMI) et la vitesse fondamentale de flamme de mélanges d'α-pinène/benzène qui sont respectivement les principaux COV détectés dans les plantes et dans les fumées de feux de forêt. Le dernier chapitre concerne l'étude stationnaire de l'accumulation de gaz dans des vallées à partir d'une maquette de forêt 1/400ème disposée dans une soufflerie. / Mediterranean firefighters cope with powerful accelerations of forest fires (AFF) whose mechanisms are not very well understood. Vegetation is the only fuel of forest fire, then we studied the gases coming from them. First, we studied the thermal degradation of four Biogenic Volatil Organic Compounds (BVOCs) thanks to a flash pyrolysis and a tubular oven. From this study and literature, we chose a representative VOC mixture to study its combustion properties. We determined Minimal Ignition Energy (MIE) and its laminar burning speed of mixtures of α-pinene/benzene that are respectively the main VOC detected in vegetation and forest fire smoke. The last chapter experiment the steady-state gas accumulation above a 1/400 V-shaped forest model.