Orientador: Edson Tomaz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-26T01:44:59Z (GMT). No. of bitstreams: 1 Fujimoto_TaniaMiyoko_M.pdf: 3195882 bytes, checksum: 017f2daada97280db73d8fb4da0b097e (MD5) Previous issue date: 2014 / Resumo: Compostos orgânicos voláteis (COV) representam uma categoria de substâncias poluentes que geram diferentes impactos ambientais. Eles são responsáveis pelo aumento das concentrações de ozônio ao nível do solo e pela formação de aerossóis orgânicos secundários. Além disso, alguns deles contribuem para a degradação do ozônio estratosférico e a ampliação do efeito estufa. Alguns componentes têm um caráter carcinogênico, teratogênico ou mutagênico. Há estudos envolvendo o tratamento dos COV pelos mais diversos métodos, tais como: incineração, adsorção e absorção. Reatores fotocatalíticos, muito estudados em aplicação em fase aquosa e com grande sucesso na oxidação de contaminantes orgânicos, aparecem como uma alternativa pouco estudada. A fotocatálise em fase gasosa usando o TiO2 como catalisador se apresenta como uma solução interessante para o tratamento de compostos orgânicos voláteis, por não requerer operação em altas temperaturas, pelo baixo custo do TiO2, por ser seletiva na absorção de radiação e por gerar como produtos da reação CO2 e água, o que dispensa demais tratamentos. Estudos demonstram que a adição de metais nobres ao TiO2 comprova uma melhoria na eficiência fotocatalítica das reações de oxidação de compostos orgânicos voláteis. Dentro deste escopo, este trabalho tem como objetivo testar a eficiência do processo de oxidação de COV em fase gasosa por fotocatálise heterogênea com catalisador de dióxido de titânio (TiO2) impregnado com 1% de paládio (Pd) sob luz ultravioleta. O método de impregnação de paládio em TiO2 pela redução com NaBH4 mostrou-se adequado pelas técnicas de caracterização por DRX, XPS, UV ¿Vis, BET, MEV e Quimissorção de H2, pois há a impregnação do metal na superfície do catalisador sem promover modificações estruturais no TiO2 e não ocorreu alterações na razão de anatase/rutilo. Por XPS indicou a presença de metal em sua forma elementar. Além disso, os resultados da oxidação dos compostos n-hexano, ciclohexano, metil-ciclohexano, n-octano e iso-octano demonstraram aumento significativo na eficiência da conversão, pois foram obtidos valores acima de 90% em tempos de residência de aproximadamente 35 s / Abstract: Volatile organic compounds (VOCs) represent a category of pollutants substances that generate different impacts. They are responsible for increase concentrations of tropospheric ozone and also the formation of secondary organic aerosols. In addition, some of them contribute to the degradation of stratospheric ozone and greenhouse gas intensification. Some components have a carcinogenic, teratogenic or mutagenic character. There are studies involving the treatment of VOCs with various methods, such as: incineration, adsorption and absorption. Photocatalytic reactors, extensively studied in aqueous and with great success to destroy organic contaminants, appears as an alternative understudied. The photocatalysis gas phase using TiO2 as catalyst shows an interesting solution for the treatment of volatile organic compounds, because does not require operation at high temperatures, the low cost of TiO2, being selective in absorbing radiation and the products of reactions are CO2 and water, which eliminates other treatments. Studies prove that the addition of noble metals on TiO2 can improve the photocatalytic efficiency in the oxidation of volatile organic compounds. Therefore, this paper aims to test the efficiency of oxidation of volatile organic compounds (VOC) in gas phase catalysts through heterogeneous photocatalysis with titanium dioxide (TiO2), and their impregnation with 1% palladium (Pd) and UV light. The method for impregnate palladium on TiO2 with NaBH4 reduction was appropriated according to techniques for characterization like XRD, XPS, UV-vis, BET, SEM and H2 chemisorption, because all analysis confirmed that the impregnation of the metal on the catalyst surface do not structurally modify TiO2, neither changes occurred in the ratio of anatase/rutile. XPS indicated the presence of metal in elemental form. The results the oxidation of compounds n-hexane, cyclohexane, methyl cyclohexane, n-octane and iso-octane indicated a significant increase in conversion efficiency; the values were above 90% at residence times around 35 s / Mestrado / Desenvolvimento de Processos Químicos / Mestra em Engenharia Química

Materiais de construção como: adesivos, selantes, aglomerados, compensados, carpetes, revestimentos de parede, isolamentos, forros acústicos etc., emitem compostos orgânicos volateis (COVs) em ambientes internos (Niu e Burnett, 2001). No caso da tinta no Brasil, Salasar (2006) indica que \"as tintas à base de solventes emitem 520 vezes mais COVs em relação às tintas à base de água\". Consequentemente aumentos significativos na concentração de poluentes químicos e biológicos do ar em ambientes internos são provocados pelas baixas taxas de troca de ar em conjunto com a emissão de COVs originados pelos materiais de construção dos ambientes internos (Gioda & Neto, 2003). O objetivo nesta pesquisa é identificar compostos orgânicos volateis nas emissões de tintas imobiliárias usadas em ambientes internos na cidade de São Carlos. O laboratório foi realizado com o equipamento de cromatografia gasosa acoplado a espectrometria de massas, com siglas GC/MS, junto com o aparelho para extração da amostra chamado de micro extração de fase sólida (SPME), para duas amostras de cada tinta sendo uma fresca (úmida) e outra seca. O laboratório GC/MS quando é utilizado com micro extração de fase sólida (SPME) é o método mais aproximado do ideal, já que permite qualificar os COVs contidos nas amostras de tinta com maior eficiência que qualquer outro método (Koziel & Pawliszym, 2001). A escolha das tintas, esmaltes e o verniz foram determinadas como aquelas de maior uso e venda entre os pintores e lojas de tintas, respectivamente, na cidade de São Carlos. Os resultados mostraram que as tintas podem chegar a emitir juntas mais de 61 compostos orgânicos voláteis, a maior parte deles causa irritação respiratória e cinco desses compostos são suspeitos de desenvolver câncer, a concentração de cada composto não foi determinada. Uma suposição é que a saúde dos pintores pode estar sendo afetada, pois eles têm contato constante com as emissões das tintas, neste sentido é preocupante que esses trabalhadores da construção civil sejam informais, pois nesta condição o risco à sua saúde pode ser agravado devido à falta de capacitação necessária sobre a utilização do material que estão manipulando. Parte do resultado da pesquisa mostra também por meio de um questionário, as marcas de tintas imobiliárias comumente usadas na cidade de São Carlos, assim como uma noção sobre as doenças que as tintas produzem. O questionário foi elaborado para 40 pessoas entre pintores e vendedores de lojas de tinta na cidade de São Carlos. As fichas de segurança de produtos químicos FISPQ correspondentes para cada tinta omitem informações sobre alguns ingredientes considerados de risco encontrados nas amostras de tintas, como por exemplo, compostos suspeitos de desenvolver câncer. É importante para o Brasil a criação com urgência de um selo ambiental confiável que garanta a baixa concentração de emissão de COVs nas tintas como produto, mediante valores quantificáveis. Se similar ao selo \"Green Seal\", o mesmo daria não só uma forma de controle sobre a emissão de COVs nos prédios senão confiabilidade e garantia. O selo será um parâmetro de exigência nas certificações ambientais para confirmar as baixas emissões de COVs nos materiais das edificações sustentáveis, que até agora são inexistentes. / Building materials such as: Adhesives, sealants, plywood, carpeting, wall coverings, insulation, acoustic ceilings etc., emit volatiles organic compounds (VOCs) in indoor environments (Niu e Burnett, 2001). In the case of the paint in Brazil, Salasar (2006) indicates that \"solvent-based paints emit VOCs 520 times as compared to water-based paint.\". Consequently significant concentration of chemical and biological pollutants from indoor air, are caused by low rates of air exchange in conjunction with the emission of VOCs originating from the construction of the indoor materials (Gioda & Neto, 2003). The objective of this research is to identify volatile organic compounds (VOC) emissions from architectural coatings used indoors in São Carlos. The laboratory was performed with gas chromatography equipment coupled to mass spectrometry with acronyms GC/MS, with the instrument for sample extraction called solid phase micro extraction (SPME) for two samples of each paint: a fresh (wet) and a dry. The GC/MS laboratory when used with solid phase micro extraction (SPME) is the closest to the ideal method, allows to qualify the VOCs contained in the paint samples more efficiently than any other method (Pawliszym & Koziel, 2001). The choice of paints, enamels and varnish were determined as those of greater use and sale among painters and paint stores, respectively, in the city of São Carlos. The results showed that the paint can issue more than 61 volatile organic compounds, most of them cause respiratory irritation and five of these compounds are suspected of developing cancer, the concentration of each compound was not determined. One of the hypotheses is that the health of painters may be being affected, as they have constant contact with emissions from paints,in this respect it is wrong that these workers of the construction are informal, because in this condition the risk to your health can be aggravated due to lack of necessary training on the use of the material. Part of the search result also shows by means of a questionnaire , the marks of paints commonly used in the city of São Carlos, as well as a notion about the diseases that produce the paints. The questionnaire was designed in 40 people between painters and sellers of paint shops in the city of São Carlos. Safety data sheets for chemicals corresponding MSDS for each paint omit some information about ingredients considered risk in samples of paints, such as examples, compounds suspected of developing cancer. It is important for Brazil to urgently create a reliable environmental seal that ensures low emission concentration of VOCs in paints and product through quantifiable values . If the seal is similar to the seal \"Green Seal\", it would not only a form of control over the emission of VOCs in buildings too reliability and warranty The stamp will be a requirement parameter in environmental certifications to confirm low emissions of VOCs in materials of sustainable buildings , which until now are nonexistent.

Submitted by Marcia Silva (marcia@latec.uff.br) on 2016-10-10T18:53:23Z No. of bitstreams: 1 Dissert Adriana Vidal França de Carvalho.pdf: 2829879 bytes, checksum: 20647d41336cf9b355d364ab38963b35 (MD5) / Approved for entry into archive by Biblioteca da Escola de Engenharia (bee@ndc.uff.br) on 2017-01-26T13:49:06Z (GMT) No. of bitstreams: 1 Dissert Adriana Vidal França de Carvalho.pdf: 2829879 bytes, checksum: 20647d41336cf9b355d364ab38963b35 (MD5) / Made available in DSpace on 2017-01-26T13:49:06Z (GMT). No. of bitstreams: 1 Dissert Adriana Vidal França de Carvalho.pdf: 2829879 bytes, checksum: 20647d41336cf9b355d364ab38963b35 (MD5) Previous issue date: 2016-04-18 / O impacto na qualidade do ar causado pela emissão de poluentes atmosféricos tem sido um problema ambiental crescente, especialmente nos centros urbanos e nas áreas industriais. O ozônio, formado por reações fotoquímicas, é um dos principais componentes do smog fotoquímico. Devido às suas características oxidantes ele é prejudicial à saúde e ao meio ambiente. Por ser um poluente secundário, o controle dos níveis de ozônio na troposfera deve ser realizado a partir da redução dos seus principais precursores: COVs e óxidos de nitrogênio. Refinarias de petróleo são importantes fontes de COVs, especialmente de emissões fugitivas de componentes de linhas de processo e, portanto, são fontes onde há potencial para reduzir estas emissões. Além disso, as licenças ambientais das refinarias também exigem a redução de emissões fugitivas de COVs. A metodologia LDAR, baseada no uso de um analisador portátil para identificação de vazamentos em componentes de linhas de processo, vem sendo utilizada nos Estados Unidos desde a década de 70 para a redução das emissões fugitivas de COVs em refinarias de petróleo. É uma metodologia bastante intensiva em mão de obra e tem custo elevado, uma vez que exige o monitoramento individual de milhares de componentes existentes em uma planta industrial para a detecção de vazamentos. Porém, estudos mostram que o controle com foco nos grandes vazamentos permite uma redução mais efetiva das emissões fugitivas e com menor custo. A metodologia Smart LDAR, que consiste no uso de imagem ótica de infravermelho para visualização de gases, permite a identificação dos grandes vazamentos, que são os que mais contribuem para as emissões fugitivas, sem que haja necessidade de medição de todos os componentes das linhas de processo. O objetivo desta pesquisa é avaliar as metodologias LDAR (Leak Detection and Repair) e Smart LDAR, utilizadas para o controle de emissões fugitivas de compostos orgânicos voláteis (COVs) em refinaria de petróleo, utilizando o conceito de custo-efetividade. Os resultados obtidos a partir das avaliações realizadas mostraram que a metodologia Smart LDAR tem melhor relação custo efetividade para o controle de emissões fugitivas de COVs em comparação à metodologia LDAR convencional / The impact on air quality caused by air pollutants emissions has proven to be a growing environmental problem, mainly at urban centers and industrial areas. The ozone, formed through photochemical reactions, is the photochemical smog’s major component. Due its oxidizing characteristics, it is harmful to the healthy and to the environment. Due to de fact to be a secondary pollutant, the ozone control in the troposphere must be achieved by reducing emissions from its main precursors: VOCs and nitrogen oxides. Petroleum refineries are significant sources of VOCs, especially of fugitive emissions from process lines’ components, so they are sources with potential to reduce these emissions. Furthermore, the petroleum refineries’ environmental licenses also demand the reduction of VOCs’ fugitive emissions. The LDAR methodology, which is based on the application of a portable analyzer to identify leaks in process lines’ components, has been used in the US since the 70s to reduce VOCs’ fugitive emissions in petroleum refineries. This methodology is quite intensive hand labor and costly, since an industrial plant has thousands of components that must be measured individually to detect leaks. However, studies show that the control focusing on large leaks allows the reduction of fugitive emissions more effectively and with low costs. The methodology known as Smart LDAR, which uses infrared optical image for gas leaks view, has the potential to identify great leaks, that most contribute to the fugitive emissions, without requirement to measure all process lines’ components. The purpose of this research is evaluate the methodologies LDAR (Leak Detection and Repair) and Smart LDAR, used to control volatile organic compounds’ (VOCs) fugitive emissions in petroleum refineries, using the concept of cost-effective analysis. The results obtained from the evaluations of this study showed that the Smart LDAR methodology has the best cost effective relation to control fugitive emissions compared to the LDAR conventional methodology

Abstract This thesis aimed at developing methods for tracking the environmental origins of microbial contaminants of the food chain. We worked on three targets: i) environmental mycobacteria ii) toxinogenic Bacillus species iii) post-harvest fungi in strawberry jam. Our aim was to develop methods for early detection of the above contaminants, which have the potential to endanger consumer health. We developed a novel method based on 16S rRNA hybridization for tracking the reservoirs of potentially pathogenic environmental mycobacteria in piggeries and soil. From 1010 to 1012 16S rRNA molecules of environmental mycobacteria were found per gram of peat, wood shavings and straw in piggeries with a high prevalence of infections. These beddings may thus be a source of mycobacteria for pigs. We found 1010–1011 of mycobacterial 16S rRNA molecules per gram of Finnish forest soil, indicating that the soil contained 107–109 mycobacteria per gram. These numbers exceed the previous cultivation-based estimates of mycobacterial content in Finnish soils. To elucidate the role of mastitis in the input of toxinogenic Bacillus into the dairy production chain, milks were sampled from mastitic cows. Twenty-three Bacillus isolates were screened for toxins using the sperm cell motility inhibition assay. Four of the six toxinogenic isolates found were identified as Bacillus pumilus and two as Bacillus licheniformis. The isolates produced toxic substances that were heat-stable (100 °C) and soluble in methanol, thus being of non-protein nature. The extracts prepared from the toxin-producing isolates disrupted the plasma membrane of exposed sperm cells at concentrations 1–15 μg ml-1 (B. pumilus) 20–30 μg ml-1 (B. licheniformis). The toxic action of the mastitis-associated B. licheniformis strains was similar to that of the lipopeptide lichenysin A. The genes for lichenysin synthetase were found in these strains by PCR. This study revealed that heat-stable toxin-producing strains of B. pumilus and B. licheniformis occur in milk of mastitic milking cows. They may enter the dairy production chain when milk of clinically healthy cows recovered from mastitis is sent to dairies. Many foodborne contaminant fungi are known to produce volatile organic compounds. We investigated the suitability of such metabolites as early indicators of fungal contamination of strawberry jam. We found that volatile organic compounds commonly produced by the contaminant fungi in strawberry jam were 2-pentanone, styrene, 3-methyl-1-butanol, 1,3-pentadiene and ethanol. The results indicate that these compounds could be used to detect fungal contamination of jam.

Abstract Volatile Organic Compounds (VOCs) in wastewaters from the chemical industry are of major concern because of their environmental and health impacts. The reclamation of VOCs from wastewaters would not only reduce the hazard to the environment but also contribute to an efficient use of resources. The thesis explores the reclamation of n-butanol and dichloromethane from sodium chloride containing mixtures by pervaporation. Another aim was to gain understanding of mass transport phenomena during the pervaporation of multicomponent systems, and the effect of sodium chloride on the pervaporation performance. In this work, the reclamation of n-butanol and dichloromethane was conducted as a sequence of pervaporation stages which utilised first hydrophobic and then hydrophilic membranes. The objective was to segregate the mixture of n-butanol/dichloromethane/sodium chloride/water into three different streams: a re-use quality concentrate of VOCs, brine, and discharge quality purified water. The effect of the experimental variables, VOCs feed concentration, feed temperature and sodium chloride content on the performance of the pervaporation stages was studied. A statistical design, response surface methodology, was used to further resource efficiency. The results indicate the potential of pervaporation for the reclamation of n-butanol and dichloromethane from aqueous mixtures. A single step of pervaporation of n-butanol/dichloromethane/sodium chloride/water systems using the CMX-GF-010-D (Celfa) and PERTHESE® 500-1 (P 500-1) membranes does not sufficiently concentrate the VOCs for direct re-use. It is also demonstrated that the electrolyte does not permeate through the membranes and does not affect their separation effectiveness significantly. The pervaporation of the water/dichloromethane/n-butanol system using the hydrophilic poly(vinyl alcohol)-titanium dioxide/polyacrylonitrile/polyphenylene sulfide (PVA-TiO2/PAN/PPS) membrane is effective for dewatering purposes. The membrane shows impermeable features towards dichloromethane in the studied conditions. The analysis of the mass transport phenomena demonstrates that, under the experimental conditions studied, the resistance towards the mass transport of the compounds through the membrane is mainly exhibited by the membrane itself. This study also shows the advantage of analysing the effect of temperature on membrane permeation by the permeation activation energy instead of by the apparent activation energy.

Dans le domaine du sport, le problème des odeurs sur les vêtements ou chaussures est récurrent et aucune solution réellement efficace n’est proposée à ce jour. Les odeurs corporelles résultent de la dégradation bactérienne de constituants de la peau et de la sueur inodore. Un textile photocatalytique a donc été développé dans le but de dégrader à la fois les odeurs et leur source bactérienne. Le composé modèle odorant choisi pour les tests photocatalytiques en phase gazeuse est l’acide isovalérique. La disparition de l’odeur a été évaluée à l’aide d’un nez électronique. L’évaluation de l’efficacité antibactérienne a été réalisée sur deux souches de micro-organismes cutanés : Staphylococcus Epidermidis et Brevibacterium Linens , selon la norme ISO 20743 adaptée à l’usage de la photocatalyse. Le textile, destiné à servir de revêtement des semelles internes des chaussures Salomon, a été imprégné de TiO2 selon différentes méthodes de dépôt (foulardage, imprégnation par transfert). La teneur en catalyseur, jouant un rôle fondamental dans l’activité photocatalytique du textile, a été optimisée afin de dégrader les composés organiques et les bactéries tout en présentant une bonne tenue du TiO2 aux tests de lavage et d’abrasion. Les résultats ont montré que quelques heures d’irradiation UV-A avec un faible éclairement énergétique (1 mW/cm2) suffisent à dégrader tout l’acide isovalérique ainsi que les micro-organismes déposés sur le textile. Ces résultats suggèrent qu’une exposition des semelles photocatalytiques à un rayonnement solaire pourrait être envisagée pour l’utilisation par les consommateurs. Des tests de terrain de porté de semelle sont en cours pour valider le transfert industriel à grande échelle / So far, the odor issue in sportswears remains unsolved. These odors produced during a physical activity come from the bacterial degradation of components from skin and odorless sweat. A photocatalytic textile has been developed in order to degrade both odors and their bacterial source. The odorant model molecule chosen for gaseous photocatalytic degradation tests is the isovaleric acid. The disappearance of odor was evaluated by using an electronic nose. Antibacterial activity was tested on Staphylococcus Epidermidis and Brevibacterium Linens strains with the ISO 20743 standard adapted for such photocatalytic tests. The textile, used as a lining for Salomon insoles, was impregnated with TiO2 according to different coating methods (padding, kiss-rolling). The TiO2 loading on the textile is a fundamental parameter in photocatalytic activity and has been optimized to degrade organic compounds and bacteria providing a good TiO2 hanging on the fibers after washing and abrasion tests. Results show that only few hours of UV-A irradiation at a low irradiance (1 mW/cm2) are sufficient to degrade all the isovaleric acid and the bacteria on the textile. These results suggest that a solar exposure of the insoles is possible for consumers use. Field tests are in progress using these insoles to validate the industrial large-scale transfer

Human scent has been the focal point of diverse scientific interests and research initiatives for the past several years. The knowledge gained about its composition has favored the advancement of multiple disciplines, and promoted the development of a wide variety of applications. Among these applications is the use of human scent as a resource for Forensic investigations, where scent profiles are often used as evidence to associate individuals to the scene of a crime. The characteristic nature of individual human scent has enabled this type of evidence to be used as a biometric tool for the differentiation of subjects. Nevertheless, the present study discusses a new perspective towards human scent's role and application in Forensic investigations. The foundation of this new perspective consists of employing human scent’s biometric quality to classify individuals using common traits. In this research study, underarm and hand odor samples were collected from Caucasian, Hispanic and East Asian individuals, of both genders. Subjects were also organized into 3 different age groups: 18-30, 35-50 and 55+ years. Headspace Solid Phase Micro-extraction Gas Chromatography Mass Spectrometry (HS-SPME-GC-MS) was used to create individual scent profiles for the evaluation of subject classification by age, gender and race/ethnicity. Individual classification was assessed through the identification of qualitative and quantitative patterns in the volatile organic compound (VOC) constituents that characterize human scent. Principal Component and Linear Discriminant analyses of the collected scent profiles, led to the identification and validation of characteristic VOC marker combinations for age, gender and race/ethnicity. Statistical analysis facilitated group classification and differentiation on the basis of these traits. Moreover, this study also evaluated the use of solvent extraction as a complementary technique to HS-SPME for human scent analysis. Findings from this assessment revealed that the simultaneous consideration of data from both extraction techniques favors an enhancement of the classification of subjects by means of human scent. The discoveries achieved in this study represent a significant step for human scent as a forensic tool. The outcome of this research has cleared a new path for further human scent investigation, and highlighted its further relevance to forensic applications.

La pollution de l'air intérieur est un enjeu majeur pour la santé humaine. Pour réduire les concentrations de polluants des milieux confinés, notre étude s'est basée sur la conception et les tests d'un nouveau média photocatalytique innovant composé de textile rendu lumineux grâce à la présence de fibres optiques microstructurées. Le textile est rendu photocatalytique après ajout de TiO2 en suivant différentes méthodes de dépôt. Les fibres optiques ont alors deux rôles fondamentaux : premièrement d'être le support du catalyseur et deuxièmement d'être le moyen d'amener le rayonnement UVA au coeur du lit photocatalytique. La rencontre des trois constituants de la photocatalyse, les photons UV, le catalyseur et le polluant, est alors favorisée par l'utilisation de ce type d'échantillon. Les propriétés structurales et optiques de ce nouveau matériau ont été caractérisées par des analyses de surface (microscopie otique et microscopie électronique à balayage environnementale (MEBE)), des mesures d'irradiance UV et des analyses permettant de localiser le TiO2 à la surface de l'échantillon (Raman et MEB‐EDX). L'influence de différents paramètres tels que la structure textile, la méthode de dépôt, les caractéristiques d'irradiation, les débits molaires sur la dégradation de deux composés organiques volatiles, le formaldéhyde et le toluène, a été étudiée et corrélée aux propriétés physicochimiques du matériau / The indoor air pollution is a major challenge for human health. To reduce the concentrations of pollutants in confined area, our study is based on the design and testing of a new innovative photocatalytic media composed of textile which is lighted with microstructured optical fibres. The textile becomes photocatalytic after the coating of TiO2 with different methods. The optical fibers have then two fundamental roles: first to be the catalyst support and secondly to be the light transmission support from the source into the photocatalytic bed. The meeting of the three constituents of photocatalysis (UV photons, catalyst and pollutants) is then enhanced by the use of this type of sample. The structural and optical properties of this new material were characterized by surface analysis (optical microscopy and electronic secondary electron microscopy (ESEM)), with measurements of UV irradiance and methods to determinate the location of the TiO2 on the sample surface (Raman spectroscopy and EDX‐SEM). The influence of different parameters such as textile structure, coating method, irradiation characteristics, molar flow on the degradation of two volatile organic compounds, formaldehyde and toluene, was studied and correlated to the physical‐chemical properties of the material

Dans ce travail, l’effet de la présence de certaines plantes de service (PdS) à proximité d’une plante hôte (Capsicum annuum) sur le comportement et l’installation d’une population de pucerons (Myzus persicae) a été étudié afin de contribuer à la recherche de méthodes de luttealternatives et innovantes contre ces insectes.Dans une première étape, une étude bibliographique a été réalisée, à partir de la littérature etdes connaissances sur des pratiques de jardinage traditionnel afin d’identifier des PdSméditerranéennes caractérisées par leurs propriétés insecticides et surtout aphicides. Nousavons sélectionné treize PdS : Rosmarinus officinalis, Lavandula latifolia, Ocimum basilicum,Tagetes patula, Tagetes erecta, Pelargonium zonal, Calendula officinalis, Thymus vulgaris,Satureja hortensis, Mentha piperita, Allium schoenoprasum, Carthamus tinctorius, Dittrichiaviscosa. Nous avons étudié dans une deuxième étape, le comportement d’installation deMyzus persicae sur sa plante hôte en présence d’une PdS en conditions contrôlées. Lesrésultats de ces travaux ont montré que la présence de certaines espèces comme R. officinalis,T. patula, T. erecta, P. zonal, L. latifolia, O. basilicum, C. officinalis ou A. schoenoprasum,affectait la survie et /ou la fécondité des femelles au cours du temps en comparaison avec letémoin. Nous avons aussi caractérisé chaque plante par un profil de composés volatils etrechercher des relations entre ces profils de COV et l’efficacité des PdS.Ensuite nous nous sommes intéressés aux mécanismes d’action des PdS et nous avons étudiél’effet direct des PdS sur les pucerons par olfactométrie. Nous avons trouvé qu’en présence deR. officinalis, T. patula en fleur, P. zonal, L. latifolia, O. basilicum, ou M. piperita lesfemelles se dirigent préférentiellement vers l’odeur de leur plante hôte. Nous avons égalementtesté une deuxième hypothèse correspondant à l’effet des COV émis par les PdS sur la plantehôte. Pour cela les plantes hôtes ont été pré-conditionnées avec les PdS pendant 5 jours. Cepré-conditionnement a modifié le profil volatil du poivron et a eu un effet négatif surl’installation des pucerons sur les poivrons pré-conditionnés avec T. patula. Enfin, nous avonstesté l’efficacité de l’association avec R. officinalis, L. latifolia ou O. basilicum dans desconditions de cultures moins confinées (sous tunnels). Nous avons retrouvé un effetsignificatif sur le comportement du puceron de ces PdS. Dans le cas du romarin nous avonsobservé une diminution de l’efficacité de l’association lorsque l’on s’éloigne des plantes deromarin. L’efficacité maximale a été observée sur les poivrons placés à côté du romarin. Aplus grande distance, l’efficacité des PdS diminuait et n’était plus significative. Ces donnéesoffrent des nouvelles pistes de recherche en vue de l’utilisation judicieuse des PdS au sein desagroécosystèmes / In this work, the effect of intercropping companion plants (CP) near a host plant (Capsicumannuum) on the performance and the installation of an aphid’s population (Myzus persicae)was studied to contribute to the search of alternative and innovative methods of pests control.First, a bibliographic study based on the literature and traditional gardening was performed toidentify mediterranean CP characterized by their insecticidal and mainly aphicide properties.We selected thirteen CP: Rosmarinus officinalis, Lavandula latifolia, Ocimum basilicum,Tagetes patula, Tagetes erecta, Pelargonium zonal, Calendula officinalis, Thymus vulgaris,Satureja hortensis, Mentha piperita, Allium schoenoprasum, Carthamus tinctorius, Dittrichiaviscosa. In a second step, we investigated the settling of Myzus persicae on its host plantwhen intercropped with CP under controlled conditions. The results showed thatintercropping with some species such as R. officinalis, T. patula, T. erecta, P. zonal, L.latifolia, O. basilicum, C. officinalis or A. schoenoprasum, affects the survival and / or femalefecundity over time compared to the control. We also characterized each plant by a volatilecompounds profile and looked for relationships between these profiles and the effectivenessof CP. Then, we investigated the mechanisms of action of a CP. We studied the direct effectof CP on aphids by olfactometric tests. We found that, in the presence of R. officinalis,flowering T. patula, zonal P., L. latifolia, O. basilicum, or M. piperita, females prefer theodor of its host plant. We also tested a second hypothesis that VOCs emitted by a CP mayaffect the host plant. Plants were preconditioned with CP for five days. This preconditioningmodified the volatile profile of pepper but had only a negative effect on the settling of aphidson pepper preconditioned with T. patula. Finally, we tested the association with R. officinalis,L. latifolia and O. basilicum under greenhouse conditions. We found a significant effect onthe settling of aphid when using these CP and a decrease of rosemary efficiency when movingaway from rosemary plants. The larger effect was observed on peppers located close torosemary. These data provide new avenues of research and indication on judiciously CP thatcould be intercropped within agro-ecosystems

Les composés organiques volatils comme le formaldéhyde sont des polluants nocifs pour la santé humaine et leur décomposition en composés moins toxiques est fortement étudiée. Ainsi, différents catalyseurs à base d’oxyde métallique permettant une décomposition thermique efficace du formaldéhyde ont été développés. Dans cette optique, les catalyseurs à base d’oxyde métalliques sont souvent présentés comme des catalyseurs prometteurs. Ce travail consiste à préparer des catalyseurs à base de cobalt et/ou de manganèse supportés sur zircone destinés à l’oxydation du formaldéhyde. Les catalyseurs ont été synthétisés par imprégnation en excès de volume (méthode classique) en modifiant la solution métallique par ajout de cyclodextrines.Dans ce travail, différents paramètres tels que le précurseur métallique, la nature de la cyclodextrine et la quantité de cyclodextrines ont été étudiés. Un effet bénéfique de l’ajout de cyclodextrines sur l’activité catalytique est obtenu et le rôle des cyclodextrines lors de chaque étape de la préparation (dans la solution d’imprégnation, avant l’activation et après l’activation) a été abordé. Les interactions entre la cyclodextrine et le précurseur métallique en solution modifient le processus d’activation permettant ainsi la formation de petites particules plus actives.En complément à ce travail, les cyclodextrines ont également été utilisées pour préparer par précipitation assistée une zircone présentant une structure cristalline purement quadratique. La stabilisation de la phase quadratique ayant lieu grâce à la formation d’un précurseur nouveau composé de cyclodextrines incorporées dans le polymère d’oxohydroxyde de zirconium. Cette nouvelle méthode de synthèse a été adaptée pour préparer un oxyde mixte MnOx-ZrO2 qui s’est révélé particulièrement actif dans la réaction d'oxydation du formaldéhyde. / Volatile organic compounds, such as formaldehyde are currently health concern and their elimination into harmless compounds is of great importance. Different catalysts metal oxides have been developed to decompose formaldehyde under thermal treatments. The present work aims at developing cobalt and/or manganese oxides catalysts supported on zirconia designed for the deep oxidation of formaldehyde. The catalysts have been synthesized by classical wet impregnation method and the started metal solution has been modified by the controlled addition of cyclodextrins.The influence of different parameters, such as the metal precursor, the nature of the cyclodextrin nature and the amount of the cyclodextrin has been studied. A beneficial effect of cyclodextrins addition on the catalytic activity has been obtained and the role of the cyclodextrins at each stage of the preparation has been investigated (i.e. in impregnating solution, before activation and after activation). Interactions occurring in the aqueous phase between the cyclodextrin and the metal precursor modify the activation process leading to the formation of small particles size more active.As an extension, cyclodextrins have also been used to prepare by simple synthesis procedure of single-phase tetragonal zirconia. The stabilization of the tetragonal phase is suggested to occur via the formation of a composite material precursor composed of incorporated cyclodextrin within the polymeric zirconium hydroxide. Finally, the effect of the cyclodextrin modified zirconium hydroxide was adapted in the preparation of a very efficient mixed oxide MnOx-ZrO2 in the oxidation of formaldehyde.