Designing architecture is related to producing vast amounts of information based on constraints, experience or common sense, and at the same time, those designs are assisted by specialized software, but, are the results of those processes giving you advantage or are they leading you in the wrong way? For example, should you include shading elements or less glazing? Should you change the shape of the building or improve envelope specifications? This research is a start to understand how to approach to design problems related to solar geometry, recognize which variables are worth modifying, reduce potential of error when iterating, and take truly advantage of the output delivered by modeling tools. / Master of Architecture

Dans un contexte où les inquiétudes environnementales dues à la pollution sont grandissantes à l’échelle globale, la surveillance de la pollution environnementale constitue un enjeu majeur de recherche afin de préserver au mieux un environnement sain et durable. En effet, la surveillance responsable et continue de l’environnement accompagnée par le développement d’alternatives de lutte « verte » contre les nuisibles, pourrait certainement ralentir voir inhiber la propagation de polluants néfastes pour l’ensemble de la biosphère. Dans ce contexte, les objectifs principaux de cette thèse visent d’une part à caractériser la qualité de l’air par une approche basée sur le biomonitoring, et d’autre part à développer un biopesticide d’origine algale permettant la protection des agrumes en post-récolte comme un exemple d’alternative à l’usage des traitements chimiques classiques. Pour répondre au premier objectif, des méthodes d’extraction multi résidus ont dû être développées. Ces méthodes ont été soit spécifiques d’une famille de pesticides tel que les dithiocarbamates, soit plus large et plus générale en considérant de nombreux polluants comme des pesticides, des HAPs et des PCBs. Ces dernières ont été basées soit sur l’ASE-SPE-SPME, soit sur le QuEChERS-SPME, et ont formé le socle des études de biosurveillance environnementale entreprises. Ces études de surveillance ont permis l’évaluation des modifications spatio-temporelles de la qualité de l’air grâce à des espèces naturelles ayant un rôle de capteurs biologique de la pollution environnementale et permettant par la suite l’estimation de la pollution dans des zones bien définies. Pour répondre au second objectif, des extraits aqueux d’algues vertes, Ulva linza et Ulva lactuca, ont été préparés et testés comme antifongiques in vivo et in vitro afin d’étudier leur aptitude à inhiber le développement de Penicillium digitatum sur des agrumes en post récolte. Un potentiel de protection des agrumes en poste-récolte contre ce champignon a été mis en évidence, donnant effectivement l’espoir à la fiabilité de cette approche comme alternative biologique pour le remplacement des pesticides chimiques potentiellement toxiques. / In a context where environmental concerns due to pollution are growing on a global scale, monitoring of environmental pollution is a major research challenge in order to preserve as much as possible a healthy and sustainable environment. Indeed, the responsible and continuous monitoring of the environment escorted by the development of "green" pest control alternatives could certainly decelerate or even inhibit the spread of harmful pollutants into the entire biosphere. In this context, the main objectives of this thesis are intended firstly to characterize air quality by a biomonitoring-based approach and, secondly, to develop a biopesticide of algal origin, that allows the protection of post-harvested citrus fruit, as an alternative to the use of conventional chemical treatments. In order to answer the first objective, multi-residues extraction methods were developed. These methods were either specific to a family of pesticides such as dithiocarbamates or wider and more general regarding numerous pollutants such as pesticides, PAHs and PCBs. The latter were based either on the ASE-SPE-SPME, or on the QuEChERS-SPME, and formed the base of environmental biomonitoring studies undertaken. These monitoring studies allowed the assessment of spatial and temporal changes in air quality through natural species acting as biological sensors of environmental pollution and subsequently allowing the estimation of pollution in well-defined areas. To answer the second objective aqueous extracts of green algae, Ulva linza and Ulva lactuca, were prepared and tested as in vivo and in vitro antifungal agents, in order to study their ability to inhibit the development of Penicillium digitatum on post-harvested citrus fruits. A potential of post-harvested citrus fruits’ protection against this fungus was proved, giving hope to the reliability of this approach as a biological alternative for the replacement of potentially toxic chemical pesticides.

Les substances pharmaceutiques font partie du groupe des contaminants émergents du fait de leur intérêt récent dans les études environnementales comparativement à des polluants étudiés depuis plus longtemps tels que les pesticides. Elles correspondent aux principes actifs des médicaments et, à ce titre, sont responsables des propriétés pharmacologiques des médicaments. Ce sont donc des molécules biologiquement actives qui peuvent agir sur les organismes vivants présents dans les écosystèmes impactés. L’origine des substances pharmaceutiques dans l’environnement est variable mais les principales sources sont liées à leur utilisation en médecine humaine ou vétérinaire. Une fois consommées, les substances pharmaceutiques sont excrétées dans les urines ou les fèces et se retrouvent dans les eaux usées (consommation humaine) ou dans les déchets d’élevage (consommation vétérinaire). Dans le premier cas, elles peuvent être rejetées directement dans le milieu, ou indirectement, avec les eaux usées traitées ou les boues résiduaires, après traitement dans les stations d’épuration (STEP). Dans le deuxième cas, elles atteignent directement le milieu lorsque les animaux sont élevés en prairie ou indirectement lorsque les déchets d’élevage sont épandus sur les sols agricoles pour les fertiliser. Ces travaux de thèse se sont attachés à étudier l’origine et le devenir de ces substances dans ces 2 cas de figure. Ainsi en se basant sur des critères de consommation, de présence dans l’environnement par rapport à des études antérieures, de toxicité et d’écotoxicité, d’originalité et de disponibilité des composés standards de référence, 32 puis 78 molécules appartenant aux classes thérapeutiques des antibiotiques, des anticancéreux, des béta-bloquants, des anti-VIH et des inhibiteurs de phosphodiestérase de type 5 (PDE 5) ont été étudiées dans 2 continuums : i) effluents hospitaliers - eaux usées brutes et traitées – eaux de surface, et ii) eaux usées brutes et traitées - eaux de surface - eaux de captage souterraines. En s’appuyant sur les mêmes critères de sélection, le devenir de 7 antibiotiques a été étudié dans des lisiers porcins dans des filières simples de traitement du lisier (fosse de stockage), dans des filières complexes de traitement du lisier (système de traitement ressemblant à des mini STEP) et dans des mésocosmes en conditions contrôlées. Pour pouvoir réaliser l’ensemble de ces études, des protocoles analytiques mettant en œuvre une étape d’extraction par SPE (Solide Phase Extraction) ou d’extraction ASE (Extraction Accélérée par Solvant) puis de purification par SPE et d’analyse par LC/MS/MS (Chromatographie en phase liquide couplée à la spectrométrie de masse en tandem) ont été développés. Ces protocoles, en remplissant des critères de qualité tels que des limites de détection et de quantification compatibles avec des analyses environnementales (de l’ordre du ng/l à la dizaine de ng/l), une bonne linéarité, précision, justesse et performance, ont permis d’analyser la phase dissoute des échantillons d’eaux et la phase dissoute et solide des échantillons de lisiers. Il ressort des analyses des échantillons aqueux que : i) les béta-bloquants, les anti-VIH et les antibiotiques appartenant aux familles des macrolides, des fluoroquinolones et des sulfonamides, sont les molécules les plus représentatifs de la contamination du milieu naturel parmi les classes étudiées ; ii) les rejets de STEP sont une source majeure de la contamination des systèmes aquatiques ; iii) les eaux usées sont davantage contaminées en hiver qu’en été ; et iv) les eaux de surface sont davantage contaminées en été qu’en hiver. / Pharmaceutical substances belong to the group of emerging contaminants due to their recent interest in environmental studies in comparison with pollutants who have been studied for a longer time like pesticides. They correspond to the active ingredient of drugs and by this mean are responsible for their pharmacological properties. Consequently they are biologically active molecules that can act on living organisms present in impacted ecosystems. The origin of pharmaceuticals in the environment is variable but the main sources are related to their use in human and veterinary medicine. Once consumed, pharmaceutical substances are excreted in urine or feces and are found in wastewater (human consumption) or animal manure (veterinary consumption). In the first case, they can be discharged directly in the environment, or indirectly, with treated wastewater or sludge from sewage treatment plants (SWTP). In the second case, they directly reach the environment when animals are bred on grassland or indirectly when livestock wastes are spread on agricultural soils as fertilizer. This PhD work has been focused on the study of the origin and fate of pharmaceutical substances in these 2 cases. Thus according to consumption data, occurrence in the environment reported in previous studies, toxicity and ecotoxicity data, originality and availability of reference standard compounds, 32 then 78 molecules belonging to 5 different therapeutic classes (antibiotics, antineoplastics, beta-blockers, anti-HIV, phosphodiesterase type 5 inhibitors (PDE 5 inhibitors)) were studied in 2 continuums : i) hospital wastewater effluents – raw and treated wastewater – surface water, and ii) raw and treated wastewater – surface water – ground water. Based on the same selection criteria, the fate of 7 antibiotics was studied in pig manure in simple manure storage facilities (storage tank), in aerobic manure treatment facilities (treatment system like in small SWTP) and in mesocosms under controlled conditions. In order to achieve all these studies, analytical protocols implementing an extraction step by SPE (Solid Phase Extraction) or an ASE extraction (Accelerated Solvent Extraction) followed by a SPE purification and an analytical step by LC / MS / MS (liquid chromatography tandem mass spectrometry) have been developed. These protocols, by filling out quality criteria such as limits of detection and quantification compatible with environmental analysis (ng/l to dozen of ng/l), good linearity, precision, accuracy and performance, were used to analyze the dissolved phase of water samples and dissolved and solid phases of pig manure samples. The water samples analysis shows : i) beta-blockers, anti-HIV and antibiotic belonging to the families of macrolides, fluoroquinolones and sulfonamides are the most representative molecules of the environmental contamination from the classes studied; ii) SWTP releases are a major source of aquatic systems’ contamination; iii) wastewaters are more contaminated in winter than in summer; and iv) surface water are more contaminated in summer than in winter. The pig manure samples analysis shows : i) the levels of contamination of manure by antibiotics are high, from a few µg/l to mg/l; ii) the manure level of contamination is not related to the physiological stage of pigs; iii) the interest to store manure before spreading in order to reduce the antibiotics contamination is not highlighted; iv) oxytetracycline, tetracycline, tylosin and marbofloxacin are mainly present in the solid phase whereas sulfadiazine, lincomycin and monensin are mainly present in the liquid phase of manure; v) the separation of solid and liquid phases reduce manure contamination in aerobic treatment facilities; and vi) antibiotics degradation is mainly aerobic.Key words: ,

Les amplificateurs optiques à semi-conducteurs (SOA) sont des composants multifonctionnels utilisables dans des applications de plus en plus variées, notamment dans les réseaux multiplexés en longueur d'onde. Ce travail est consacré à la modélisation large-bande du comportement statique et dynamique des SOA. Le terme large-bande couvre une large plage de variation de la longueur d'onde des signaux optiques incidents, de leur puissance, ainsi qu'une large plage de variation du courant d'alimentation électrique des SOA. Cette modélisation large-bande a été validée pour plusieurs SOA, à la fois pour le gain, l'émission spontanée ampliée (ASE) et le facteur de bruit (NF). Notre modélisation s'est de plus avérée cascadable puisqu'elle a permis de simuler le comportement de deux SOA en série. Notre modélisation a ensuite été étendue à la prise en compte de l'ondulation du gain et de l'ASE, à la prise en compte de l'état de polarisation des signaux et de l'ASE, du mélange à quatre ondes (FWM), des SOA à gain bloqué (GC-SOA) et à celle des SOA à gain élargi par l'insertion d'un filtre coupe-bande. Nous nous sommes aussi attachés à la modélisation dynamique du comportement des SOA en prenant en compte la compression du gain. Nous avons pour cela développé une écriture sous forme de retard complexe de l'équation de propagation facilement intégrable. Notre modèle permet ainsi de simuler le comportement des SOA jusqu'au régime picoseconde. Enn, nous avons mis en place la prise en compte des formats de modulation complexes an de pouvoir insérer notre modèle dans un environnement système.

Made available in DSpace on 2014-12-17T14:13:56Z (GMT). No. of bitstreams: 1 CarlosAAG.pdf: 323369 bytes, checksum: 093c86d6d5662ee9fb5d64b4afd66037 (MD5) Previous issue date: 2004-02-19 / The objective of this study is to estimate the prevalence of Ocular Toxocariasis, Diffuse Unilateral Subacute Neuroretinitis (DUSN), Toxoplasma gondii infection and Ocular Toxoplasmosis in a student population in Natal-RN/Brazil and relate it to demographic, epidemiologic and socio-economic risk factors. The incidence of DUSN was observed in patients at the Federal University of Rio Grande do Norte Ophthalmology Service and the Prontoclinica de Olhos Ophthalmology clinic in Natal. In cases where a worm was found in the subretinal space, the result of treatment with photocoagulation using Green Laser (Eye Light ALCON) was evaluated in relation to final visual result. The sample was randomly selected among the schools of the four districts of Natal, according to the type of institution (public or private), its level (elementary or secondary), and study period (morning, afternoon or evening). The school population was studied from March to May, 2001. Initially, the students answered a questionnaire to evaluate demographic, epidemiologic and socio-economic risk factors. Afterwards, the following procedures were carried out: blood samples were taken for Toxoplasmosis (IgG, IgM) serology, hemogram, ophthalmological examination, consisting of clinical history, measurement of visual acuity, refraction under cycloplegia, biomicroscopy of the anterior segment and annexa, funduscopy and examination of extrinsic motility. The prevalence of Toxocariasis was 0.2% or 2 per one thousand students. The sample was insufficient to estimate the prevalence of DUSN. Seventy patients with DUSN diagnosis were examined from January, 2001 to January, 2003. A live worm was found in the subretinal space of all four patients in the acute phase, and these were treated with laser photocoagulation. After follow-up (average = 11.5 months), visual acuity improved in three eyes and remained unaltered in one eye. Worms were found in 22 of the 66 patients in the chronic phase, and these also were treated with laser photocoagulation. After a follow-up period of 13.1 months, on average, visual acuity improved in two of the patients, remained unchanged in 19 and worsened in one. The comparison of visual result before and after treatment was not statistically significant (p = 0.302). The diagnosis of DUSN in the acute phase, followed by prompt localization and destruction of the worm by photocoagulation, can improve the patient s vision. However, destruction of the worm by laser photocoagulation in eyes with DUSN in the chronic phase does not improve visual acuity. Seroprevalence for IgG was 46% (Confidence Interval CI 95%-42.9-49.2%) and for IgM it was 1.4% (CI 95% = 0.8-2.4%). The prevalence of ocular lesion was 1.15% (CI 95% = 0.6 - 2.0%). Socio-economic conditions were determinants in the prevalence of Systemic and Ocular Toxoplasmosis in the bivaried analysis and confirmed in the multivaried analysis (mother s scholarity illiterate/ OR = 2.9 and p < 0.001). The T. gondii infection prevalence, although high, was less than that found in studies performed in the South and Southeast of Brazil and that of Ocular Toxoplasmosis was completely discrepant, varying from 5 to 17 times less. Although important epidemiological variables such as owning a cat, drinking unfiltered water, and coming into contact with rivers or lakes showed an association in the preliminary analysis, they lost their influence when included in the logistic model. Future studies are scheduled to begin in March, 2004, in collaboration with other Brazilian and American universities in an attempt to discover the reason for these findings, as well as identifying the different strains of Toxoplasma gondii, and studying the sources of water utilized by the population of Natal Brazil / Esta pesquisa teve como objetivo, estimar a preval?ncia da Toxocar?ase Ocular, Neuroretininte Sub-aguda Difusa Unilateral (DUSN), Infec??o pelo Toxoplasma gondii e Toxoplasmose Ocular na popula??o de escolares de Natal-RN/Brasil e relacion?-la aos fatores de risco demogr?ficos, epidemiol?gicos e socioecon?micos. Estudar a incid?ncia de DUSN em pacientes atendidos no Servi?o de Oftalmologia da Universidade Federal do Rio Grande do Norte e Prontoclinica de Olhos, em Natal, bem como, avaliar, nos casos em que foi encontrada larva no espa?o sub-retiniano, o resultado do tratamento com fotocoagula??o utilizando o Laser Verde (Eye Light ALCON) em rela??o ao resultado visual. A amostra foi selecionada aleatoriamente e distribu?da nas escolas dos quatro distritos da cidade de Natal de acordo com a natureza da institui??o (p?blica ou privada), seu n?vel (fundamental ou m?dio) e turno em que o escolar estudava (matutino, vespertino ou noturno). A popula??o de escolares foi estudada no per?odo de mar?o a maio de 2001. Inicialmente, responderam a um question?rio para avalia??o de fatores de risco demogr?fico, epidemiol?gico e socioecon?mico. Depois foram feitos os seguintes procedimentos: coleta de sangue para realiza??o de sorologia para Toxoplasmose (IgG, IgM), hemograma, exame oftalmol?gico constando de hist?ria cl?nica, medida da acuidade visual, refra??o sob cicloplegia, biomicroscopia do segmento anterior e anexos, fundoscopia e exame da motilidade extr?nseca. A preval?ncia de Toxocar?ase foi de 0,2% ou 2 por mil escolares. A amostra n?o foi suficiente para estimar a preval?ncia de DUSN. Foram examinados 70 pacientes com diagn?stico de DUSN, no per?odo de janeiro de 2001 a janeiro de 2003. Foi encontrada larva viva no espa?o sub-retiniano de todos os quatro que se encontravam na fase aguda, e tratados com fotocoagula??o a laser. Ap?s acompanhamento dos pacientes (m?dia = 11,5 meses), a acuidade visual melhorou em tr?s olhos e permaneceu inalterada em um olho. Dos 66 pacientes na fase cr?nica, foi encontrada larva em 22 deles e tratados com fotocoagula??o a laser. Ap?s acompanhamento por um per?odo de 13,1 meses em m?dia, a acuidade visual melhorou em dois, permaneceu a inicial em 19 e diminuiu em um paciente. A compara??o do resultado visual antes e ap?s o tratamento, n?o foi estatisticamente significante (p = 0,302). O diagn?stico de DUSN na fase aguda, seguida por pronta localiza??o e destrui??o da larva por fotocoagula??o, pode melhorar a vis?o dos pacientes. No entanto, a destrui??o da larva por fotocoagula??o a laser em olhos com DUSN, na fase cr?nica, n?o melhora a acuidade visual. A soropreval?ncia para IgG foi de 46% (Intervalo de Confian?a -IC 95% - 42,9-49,2%) e para IgM foi 1,4% (IC 95% = 0,8-2,4%). A preval?ncia de les?o ocular foi 1,15% (IC 95% = 0,6 2,0%). As condi??es socioecon?micas foram determinantes na preval?ncia da Infec??o pelo T. gondii e Toxoplasmose Ocular na an?lise bivariada e confirmada na an?lise multivariada (escolaridade da m?e n?o alfabetizada/OR = 2,9 e p< 0,001). A preval?ncia de Toxoplasmose Sist?mica, embora elevada, foi menor do que a encontrada em estudos realizados no Sul e Sudeste do Brasil e, a da Toxoplasmose Ocular foi totalmente discrepante, variando de 5 a 17 vezes menos. Embora importantes vari?veis epidemiol?gicas, tais como possuir gato, beber ?gua n?o filtrada, ter contato com lagoas ou rios, tenham mostrado associa??o na an?lise preliminar, perderam sua influ?ncia quando inclu?das no modelo log?stico. Estudos futuros j? est?o planejados para ter inicio em mar?o pr?ximo, em colabora??o com outras Universidades do Brasil e dos Estados Unidos com a finalidade de encontrar a raz?o destes achados, bem como, identificar diferentes tipos de cepas do Toxoplasma gondii, e estudar as fontes de ?gua utilizadas pela popula??o de Natal-RN

Made available in DSpace on 2014-12-17T14:16:35Z (GMT). No. of bitstreams: 1 WalicyranisonPS_DISSERT.pdf: 2780035 bytes, checksum: 20a70f53e533bfb0816b6d9b02b8af32 (MD5) Previous issue date: 2013-06-11 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Candida albicans is a diploid yeast that in some circumstances may cause oral or oropharyngeal infections. The investigation of natural products is mandatory for the discovery of new targets for antifungal drugs development. This study aimed to determine the genotypes of 48 clinical isolates of C. albicans obtained from the oral cavity of kidney transplant patients from two distinct geographic regions of Brazil. In addition, we investigated three virulence factors in vitro: phospholipase activity, morphogenesis and the ability to evade from polymorphonuclear neutrophils. The expression of these virulence factors in vitro was also investigated in the presence of the crude extract of Eugenia uniflora. The genotype A was the most prevalent (30 isolates; 62.5%), followed by genotype C (15 isolates; 31.5%) and genotype B (3 isolates; 6.25%). When microsatellite technique with primer M13 was applied, 80% of the isolates from the South were placed within the same cluster. All Genotype C strains were grouped together within two different clusters. Genotype C was considered more resistant to PMNs attack than genotypes A and B. Strains isolated from the South of Brazil showed higher ability to combat PMNs phagocytosis. We found a high rate of genotype C strains isolated from the oral cavity of this group of patients. The crude extract of E. uniflora inhibited proper hypha formation and phagocytosis by PMNs, but had no significant effect on phospholipase activity. This study characterized oral C. albicans strains isolated from kidney transplant recipients and will contribute for the better understanding of the pathogenesis and alternative therapeutics for oral candidiasis / Candida albicans ? uma levedura dipl?ide que em certas circunst?ncias pode causar infec??es da cavidade oral e da orofaringe. A investiga??o de produtos naturais ? fundamental para a descoberta de novos alvos para o desenvolvimento de drogas antif?ngicas. Este estudo objetivou determinar os gen?tipos de 48 isolados cl?nicos de C. albicans obtidos da cavidade oral de pacientes transplantados renais de duas distintas regi?es geogr?ficas do Brasil. Al?m disso, foram investigados tr?s fatores de virul?ncia in vitro: atividade de fosfolipase, morfog?nese e a capacidade de escapar do ataque de neutr?filos polimorfonucleares. A express?o destes fatores de virul?ncia tamb?m foi investigada na presen?a do extrato bruto de Eugenia uniflora. O gen?tipo A foi o mais prevalente (30 isolados; 62,5%), seguido do gen?tipo C (15 isolados; 31,5%) e do gen?tipo B (3 isolados; 6,25%). Quando a t?cnica do microssat?lite com o primer M13 foi empregada, 80% dos isolados da regi?o Sul foram agrupados no mesmo cluster. Todos os isolados do gen?tipo C foram agrupados juntos em dois diferentes clusters bem definidos. Isolados do gen?tipo C foram considerados mais resistentes ? a??o de PMNs do que os dos gen?tipos A e B. As cepas isoladas do Sul do Brasil demonstraram maior habilidade em combater a fagocitose por PMNs. Encontrou-se uma alta taxa de isolados do gen?tipo C da cavidade oral deste grupo de pacientes. O extrato bruto de E. uniflora inibiu a forma??o de hifa e fagocitose por PMNs, mas n?o apresentou efeito significativo na atividade de fosfolipase. Este estudo caracterizou isolados cl?nicos de C. albicans da cavidade oral de pacientes transplantados renais, contribuindo para um melhor entendimento da patog?nese e terap?utica alternativa para a candid?ase oral

Ce travail de recherche a pour but d’étudier des matériaux cimentaires soumis à des attaques sulfatiques selon trois différentes conditions : attaques sulfatiques externes (ASE), formation différée d’ettringite communément appelée attaque sulfatique interne et l’effect couplé des deux réactions, ainsi que de proposer un mécanisme uniforme pour les dégradations causées par ces réactions. En se basant sur le mécanisme proposé, un model poro-mécanique est proposé pour simuler l’expansion induite par les produits expansifs néoformés pendant la dégradation. Cette étude inclut trois parties : dans la première partie, les dégradations des éprouvettes de pâte de ciment correspondant à deux types de ciments (CEM I et CEM III) et deux dimensions exposées à trois différents types d’attaques sulfatiques (ASE, ASI, et le couplage des deux réactions), sont étudiés et comparés : variations de longueur, de masse, ainsi que des observations visuelles. Les éprouvettes exposées au couplage ASE-ASI montrent la cinétique d’expansion la plus rapide et le degré de dégradation le plus important, comparé aux autres cas. Ensuite, la structure poreuse des pâtes de ciment avant et après les attaques sulfatiques est caractérisée en utilisant différentes techniques : porosimétrie à mercure (MIP), sorption dynamique de vapeur (DVS), porosité accessible à l’eau ou essais de dissolution par traitement thermique. En comparant les variations de la distribution de la taille des pores des pâtes de ciment exposées à différentes conditions, les cristaux néoformés se trouvent précipités à la fois dans les pores capillaires et les pores des C-S-H. En plus de l’évolution de la distribution de la taille des pores pendant l’ASI, un mécanisme de dégradation est proposé : les cristaux néoformés (l’ettringite) sont précipités dans les grands pores, sans provoquer une expansion manifeste, et ils sont ensuite précipités dans les pores capillaires et les pores des C-S-H, ce qui induit un gonflement. Par ailleurs, le volume des pores occupé par les produits de l’ASI sont libérés après des essais de dissolution par traitement thermique, ce qui confirme la formation de produits d’expansion dans cette gamme de pores. Enfin, en se basant sur les résultats expérimentaux montrant que l’ettringite se forme en allant des grands pores vers les plus petits, un model poro-mécanique est proposé pour simuler l’expansion des matériaux cimentaires soumis à des attaques sulfatiques. Le modèle est basé sur la croissance contrôlée en surface et les propriétés physicochimiques pour l’ASE et l’ASI, malgré les différences entre ces deux réactions. Deux constantes indépendantes : ai et ap sont proposées pour représenter la cinétique de l’invasion des cristaux et la déformation. De plus, le modèle peut être couplé avec toutes les théories mécaniques, par exemple : l’élasticité, la plasticité, la théorie de l’endommagement ou autres. Le modèle illustre bien le processus de cristallisation et il prédit l’expansion correspondante à la fois à l’ASE et l’ASI / This work aims to study cement-based materials subjected to sulfate attacks in three different conditions: External Sulfate Attack (ESA), Delayed Ettringite Formation (DEF) and the Coupling effect of both, and to propose the same damage mechanism for all of them. Based on the proposed mechanism, a poromechanical model is established to simulate the expansion induced by expansive crystals during the degradation. The study includes the following three parts. In the first part, the degradation of cement paste specimens with two kinds of cement type (CEM I and CEM III) and two dimensions (2 2 12 cm3 and 11 11 22 cm3) exposed to three sulfate attack conditions (ESA, DEF, and Coupling effect) are studied and compared, including the length variation, mass variations, and observations. The specimens exposed to the coupling effect show the fastest kinetics and the most serious degree of degradation compared to the other cases. Then, the pore structure of cement pastes before and after sulfate attacks is characterized via different techniques: MIP, DVS, water accessible tests and heat-based dissolution tests. By comparing the variation of pore size distribution of cement pastes exposed to different conditions, the generated crystals are found to be precipitated both in capillary and gel pores. In addition to the evolution of pore size distribution during DEF, a damage mechanism is proposed: the generated crystals (ettringite) precipitate in the big pores without inducing an obvious expansion, and then penetrate into capillary and gel pores, which leads to a swelling. Moreover, the pore volume occupied by DEF induced products is released after heat-based dissolutiontests, which further confirms the formation of expansive products in that porerange. Finally, based on the experimental conclusion that ettringite forms through the large to small pores in all cases, a poromechanical model is proposed to simulate the expansion of cement-based materials submitted to sulfate attacks. The model is based on the surface-controlled growth and physicochemical properties both for ESA and DEF, despite the different source of sulfate ions. Two independent constants, ai and ap, are proposed to represent the kinetics of crystal invasion and deformation. Moreover, the model could be coupled with any mechanical theories, e.g. elasticity, plasticity, damage theory or any other. The model well illustrates the crystallization process and well predicts the corresponding expansion both in ESA and DEF

Soil that is heavily contaminated with polycyclic aromatic hydrocarbons (PAHs) is often found at the sites of former gasworks and wood-impregnation plants. Since PAHs are toxic these sites represent a hazard to human health and the environment, and therefore they need to be treated, preferably by a method that destroys the contaminants, and thus eliminates the problem permanently. However, during biological and chemical degradation of PAHs other toxic compounds may be formed. If these transformation products are sufficiently persistent they could potentially accumulate during remedial processes. In the work underlying this thesis the degradation and transformation of PAHs were studied in three remedial processes: viz. a pilot-scale bioslurry reactor, microcosms with wood-rotting fungi and lab-scale treatments with Fenton's reagent. A group of transformation products referred to as oxygenated-PAHs (oxy-PAHs) was found to be particularly important, as these compounds are toxic and were shown to be relatively persistent in the environment. The oxy- PAHs were, for instance, found at significant concentrations in the gasworks soil used in most of the studies. This soil was highly weathered and had therefore been depleted of the more readily degradable compounds. In addition, experiments in which earthworms were exposed to the gasworks soil showed that the oxy-PAHs were more easily taken up in living organisms than PAHs. To facilitate the studies, new extraction and fractionation methods were developed. For instance, pressurized liquid extraction (PLE) was investigated for its reliability and efficiency to extract PAHs and oxy-PAHs from soil. Furthermore, a selective PLE-method was developed that can simultaneously extract and separate the PAHs and oxy-PAHs into two different fractions. This was accomplished by adding a chromatographic material (silica or Florisil) to the extraction cell. Under certain conditions all three remedial processes resulted in increasing amounts of oxy- PAHs in the soil. For example, 1-acenaphthenone and 4-oxapyrene-5-one accumulated in the bioslurry reactor. Similarly, in the soil inoculated with a white-rot fungus 9-fluorenone, benzo[a]anthracene-7,12-dione, 4-hydroxy-9-fluorenone and 4-oxapyrene-5-one accumulated. Finally, in an ethanol-Fenton treatment the concentration of some PAH-quinones increased in the soil. The results show that it might be necessary to monitor oxy-PAHs as well as PAHs during the remediation of PAH-contaminated sites. Otherwise, the soil may be considered detoxified too early in the process. In the long term it would be desirable to include analyses with sufficient marker compounds to follow the possible production and elimination of the oxy-PAHs. However, until such compounds can be identified it is suggested that contaminated soil should be screened for oxy-PAHs in general. The selective PLE-method presented in this thesis could be a useful tool for this.

This study deals with corporate social responsibility (CSR) and focuses on managerial perceptions of CSR at McDonald’s South Africa (SA) and how social responsibility is translated into social practices. The key objectives of the research are: to analyse McDonald’s both internationally and locally in South Africa to establish whether CSR policies exist, then to investigate how these policies are perceived and integrated by outlet managers. Lastly to investigate what kind of social responsibility (SR) involvement, if at all, occurs at outlet level. The research site covers three regions in South Africa, which are the Eastern Cape, Western Cape and Gauteng. The total research sample is 38. 33 interviewees were outlet managers, who were purposively selected, and 5 additional interviews took place with: 2 McDonald’s SA Head Office representatives, 2 interviews with beneficiaries of McDonald’s SR involvement and 1 with the trade union SACCAWU. The research was carried out through questionnaires and semi-structured interviews. The design of this research is based on an interpretive social science approach. The aim of the research was to investigate outlet managers’ perceptions of CSR and social practices present at McDonald’s SA outlets. The key findings of the research indicate that: CSR policies at McDonald’s SA head office are not communicated sufficiently to outlet managers, SR involvement is evident, especially for initiatives focusing on children’s welfare, but far too little occurs at the outlet level. There are also too few checks on social involvement by head office and no formal reporting system is available to the outlets except through an internal magazine, called the Big Mag. There is no official CSR report at McDonald’s SA. The fact that no report exists makes this study more relevant since this research investigates matters pertaining to CSR and social practices. The overall significance of the study is that it brings to the forefront the importance of internal company and external broader regulation which is part of the greater debate of CSR. This is because the analysis of managerial perceptions and implementation of CSR shows some unwarranted discrepancies between policies and practices, locally, nationally and internationally even within the same organisation.

Made available in DSpace on 2009-11-18T18:50:27Z (GMT). No. of bitstreams: 1 TESE MC - volume I.pdf: 909223 bytes, checksum: cc5990de43a280b0ad4d88104dd1513a (MD5) Previous issue date: 2004 / In the recent years Corporate Social Action (CSA) has become more and more relevant to corporate context. The aim is to benefit both poor communities and the donnor companies, as it meets the needs of their salient stakeholders. Nevertheless, there still exists considerable scepticism concerning CSA. In order to become a solid management practice, it is critcal to evidence the attained results. Up to now, the focus has been on process evaluation, that is, on the policies companies are adopting. Literature revision has shown a great need of studies related to results identification in this field. Therefore, using stakeholders` framework (according to Wood, 1991; Donaldson and Preston, 1995; Hopkins, 1997; Hamil, 1999), we have developped a methodology to evaluate CSA results, based on public and private effectiveness criteria. As we applied it to assess Xerox social action in Brazil we were able to identify the attainment degree of expected results related to the benefitted community (Mangueira) and also to some Xerox salient stakeholders (employees and clients). / Nos últimos anos, a ação social das empresas (ASE) vem cada vez mais ganhando relevância no contexto corporativo. A expectativa é de que essa ação possa beneficiar tanto as comunidades carentes como a própria empresa, na medida em que atenda aos interesses dos seus stakeholders relevantes. No entanto, ainda existe considerável ceticismo quanto à ASE. Para que ela se torne uma prática de gestão sólida, torna-se fundamental evidenciar os resultados alcançados. Até o momento, o foco das avaliações tem sido no processo, ou seja, nas medidas que as empresas vêm tomando. Por outro lado, a revisão da literatura apontou a grande carência de estudos no que diz respeito à identificação de resultados nessa área. Assim, utilizando o enfoque dos stakeholders (Wood, 1991; Donaldson e Preston, 1995; Hopkins, 1997; Hamil, 1999), desenvolvemos uma metodologia para avaliar os resultados da ASE com base nos critérios da eficácia pública e da eficácia privada. Quando a aplicamos para avaliar a ação social da Xerox no Brasil, pudemos identificar o grau de alcance dos resultados esperados para a comunidade atendida (Mangueira) e para alguns dos seus stakeholders relevantes (funcionários e clientes).