Les écosystèmes prairiaux sont soumis à une pression anthropique, essentiellement liée à la gestion agricole, qui permet de maintenir ces milieux ouverts. Cependant, lorsque cette pression s’avère trop importante, elle peut conduire à une diminution de la diversité de la communauté végétale et, en outre, de toutes les communautés qui en dépendent (de consommateurs primaires et secondaire notamment). La biodiversité jouant un rôle reconnu pour la réalisation de diverses fonctions et services écosystémiques dont les sociétés humaines tirent profit chaque jour, les pressions anthropiques fortes peuvent altérer le maintien de ces services.Afin d’obtenir des informations complémentaires sur la réponse des communautés végétales aux différents facteurs anthropiques, il est nécessaire d’intégrer la complexité de la notion de diversité, et notamment inclure les facettes taxonomiques, phylogénétiques et fonctionnelles. Par ailleurs, l’échelle spatiale doit être considérée, en comparant les composantes alpha (intra-site) et beta (inter-sites) de la diversité gamma d’une parcelle ou d’une région.Dans ce projet, une attention particulière a été portée sur la complémentarité de ces approches de la diversité afin de rendre compte de la réponse des communautés végétales du massif jurassien aux modes de gestion agricoles pratiqués dans cette région. La production de différentes AOP fromagères, dont le Comté, offre un cadre original puisque l’existence d’une telle production implique des restrictions concernant la conduite agricole des surfaces prairiales aux exploitants. Nous avons étudié la végétation de 48 parcelles du massif jurassien réparties selon un gradient altitudinal (Premier plateau, Deuxième plateau, Haute-Chaîne) par le biais d’un protocole multi-échelle original pour des surfaces équivalentes à 0,01, 1, 10 et 1000 m². Sur ces mêmes parcelles, les pratiques agricoles ont été renseignées grâce à des enquêtes réalisées auprès des exploitants ; les conditions édaphiques ont elles aussi été étudiées grâce à des sondages de profondeur du sol et des analyses physico-chimiques réalisées sur des prélèvements dans l’horizon de surface.[...]En comparant la composition floristique de 150 relevés réalisés dans les années 1990 avec de nouvelles prospections réalisées en 2012 sur les mêmes surfaces, d’importants changements de la composition floristique sont apparus pour chacune des prairies. La tendance générale pour l’ensemble des parcelles suggère que les communautés actuelles sont davantage adaptées aux défoliations fréquentes et/ou intenses, présentent despréférences écologiques pour les milieux riches en substances nutritives et valeur pastorale plus élevée. La diversité phylogénétique s’avère également différente entre les deux sessions (ce qui n’est pas le cas de la diversité taxonomique de Simpson) et témoigne ainsi d’une réduction de la diversité des lignées avec le temps.[...]L’accumulation de phosphore dans les sols prairiaux, associée aux apports croissants d’azote apportés notamment par les engrais minéraux de synthèse, sont parmi les causes potentielles de ces changements. Bien qu’aucune diminution significative de la diversité taxonomique n’ait été enregistrée dans nos travaux, les changements de composition fonctionnelle déjà observés pourraient à l’avenir aboutir à une érosion de la diversité.[...] / Grassland ecosystems are submitted to human pressure, especially due to agricultural management, preventing their natural succession toward the forest. However, when this pressure become too important, it could lead to a decrease of the diversity of plant communities (especially primary and secondary consumers) and of all communities that depend on them. As biodiversity is recognized to play an important role in the realization of ecosystem functions and services that benefit to human societies every day, important anthropic pressures could alter the maintaining of these services.In order to provide complementary information on the response of plant communities to anthropogenic factors, it is necessary to take into account the complexity of biodiversity, especially by including the various taxonomic, phylogenetic and functional facets of diversity. In addition, the spatial scale has to be taken into account, by comparing alpha (intra-site), beta (inter-site) components of the gamma diversity of a given parcel or region:.In this project, we especially focused on the complementarity of these approaches to diversity in order to assess the response of plant communities of the French Jura Mountains to agricultural practices used in this area. The production of PDO cheese, and especially the Comté cheese, offers an original framework for such investigations as the existence of this production is associated to strict regulations imposed to farmers for the management of their grassland systems. We studied the vegetation of 48 grasslands, split according to an altitudinal gradient (First Plateau, Second Plateau, High Range) by using an original multi-scale sampling design with plot sizes of 0.01, 1, 10 and 1000 m². The agricultural practices used on these 48 parcels have also been recorded by submitting questionnaires to farmers. In addition, we collected data on soil conditions in each parcel, including soil depth and physico-chemical analyses performed on 0 – 10 cm superficial soil samples.[...]The comparison of the species composition of 150 phytosociological relevés recorded in the 1990’s and repeated in 2012 reveals important changes in the floristic composition of grasslands. The general trend observed for the overall set of relevé suggests that contemporary communities are more adapted to frequent and/or intense defoliations, have a higher pastoral value and indicate a higher level of nutrient content in the soil. We also record differences in phylogenetic diversity values between the two sessions of relevés (while the taxonomic diversity of Simpson do not change) and so show that a loss of phylogenetic lineages among time.[...]The accumulation of phosphorous in the soil, associated to increasing nitrogen supply, especially in the form of inorganic fertilizers, can partly explain this trend. Even though we do not record any significant reduction of taxonomic diversity, the functional changes already observed suggest that the diversity could potentially decrease in the future.[...]

Les fromages d’«Appellation d’Origine Protégée» (AOP) présentant un cahier des charges précis sont garants d’un savoir-faire, d’une tradition et d’un lien avec le terroir et sont également reconnus pour leurs qualités organoleptiques. Malgré une bonne implantation au niveau du marché et une consommation non négligeable, certains fromages AOP voient leurs ventes baisser. Pour dynamiser certains de ces fromages, notamment les fromages à pâte persillée, leur utilisation comme « fromages ingrédients » s’avérerait pertinente. Ce nouveau segment, très porteur pour les fromagesindustriels, consiste à les utiliser dans des préparations culinaires aussi bien à chaud qu’à froid. L’objectif des travaux de cette thèse est de réaliser d’une part un focus sur les propriétés sensorielles des fromages à pâte persillée AOP du Massif central, induites par le chauffage et plus particulièrement de la Fourme d’Ambert, en étudiant les fractions solubles de ces fromages, d’un point de vue biochimique et sensoriel, et d’autre part de connaître les préférences des consommateurs vis-à-vis des fromages à chaud. Dans un premier temps, un screening sur le comportement à chaud de différentes catégories de fromages à pâte persillée a conduit à identifier des différences texturales et gustatives et de ce fait, à catégoriser les fromages selon leurs aptitudes culinaires. Ce positionnement sensoriel a ainsi permis de sélectionner un « fromage modèle » : la Fourme d’Ambert. Dans une seconde phase, l’étude des fractions solubles a confirmé sa contribution relative dans la perception gustative des fromages à pâte persillée. Toutefois, aucune différence sensorielle n’est observée sur les fractions suite au traitement thermique malgré quelques différences sur la teneur de certains composés sapides. Enfin, la dernière phase a consisté à identifier les préférences des consommateurs vis-à-vis de la Fourme d’Ambert à froid et à chaud. Quelle que soit la température, le fromage est bien apprécié par les consommateurs. La segmentation des consommateurs révèle des perceptions différentes selon trois groupes : un groupe avec des préférences pour des fromages très typés, à l’inverse, un groupe ayant une attirance pour les fromages ayant des flaveurs moins prononcées et un dernier, axé sur les préférences des fromages à chaud. Corrélées aux profils sensoriels, aux commentaires libres des consommateurs et à leurs attentes, certaines variables sensorielles ou comportementales ont pu expliquer ces différences de préférences. Ces résultats montrent l’intérêt de l’usage de certains fromages à pâte persillée AOP en tant que « fromages ingrédients » présentant de bonnes aptitudes culinaires, par leurs propriétés fonctionnelles et gustatives. L’acceptation des fromages à chaud par les consommateurs renforce le fait que les fromages AOP peuvent être utilisés aussi bien à froid qu’à chaud, permettant ainsi l’innovation dans la filière. / PDO cheeses through their specifications are recognized for a quality in relation to a geographical origin, technical know-how, and a typical gustative quality. Despite a good consumption of PDO cheeses, the marketed volumes decreased for most of them. In order to make them more attractive, some cheeses as Blue cheeses could be used as “cheeses ingredient”. Cheeses are usually consumed at the end of a meal but a new trend is emerging: cheeses are more and more used in culinary preparations, both hot (pizza, gratin, sauce) and cold (sandwiches, salads). The main objective of this study was to firstly highlight the impact of heating on sensory properties of French PDO Blue cheeses and more particularly Fourme d’Ambert. The water-soluble fraction which plays an important role in the favour of cheeses was secondly studied in order to evaluate the impact of heating on this extract. The last objective consisted in measuring the consumers liking towards cold and heated cheeses. Therefore, sensory and biochemical methods were performed to describe crude cheeses and liking. The first study highlighted the impact of heating on both textural properties and flavour of four PDO blue-type cheeses. The main results showed that PDO cheeses present different culinary properties and thus are compatible with a use into hot preparations. The first step allowed to select a model cheese: Fourme d’Ambert. The second step consisted in studying the impact of heating on the crude cheeses and on the water-soluble fraction. In parallel, the gross composition was performed on soluble fractions and cheeses according to heating treatment. Although no treatment difference was observed on the water-soluble fraction gustatory profile, a slight difference was showed on certain chemical constituents between the water-soluble extracts. The last step was focused on the consumers liking towards cold and heated cheeses. The results showed that cheeses were much appreciated whatever heating treatments highlighting a slightly preference towards heated cheeses. Moreover, 3 groups of consumers were formed based on different preferences. One group preferred heated cheeses while two others groups preferred cold cheeses. Consumers’ group preferences were explained by means of sensory profiles and open-ended questions responses.Finally, this study shows the opportunities of new culinary uses for Blue cheeses. Sensory methods application had allowed to provide detailed information on heating properties of blue cheeses. In addition, consumers’ acceptance reinforce that PDO cheeses can be used in cold or heated preparations.

As programs continue to increase in size, it has become increasingly difficult to separate concerns into well localized modules, which leads to code tangling- crosscutting code spread throughout several modules. Thus, Aspect-Oriented Programming (AOP) offers a solution to creating modules with little or no crosscutting concerns. AOP presents the notion of aspects, and demonstrates how crosscutting concerns can be taken out of modules and placed into a centralized location. In this paper, a taxonomy of aspect-oriented programming, as well as a basic overview and introduction of AOP, will be presented in order to assist future researchers in getting started on additional research on the topic. To form the taxonomy, over four-hundred research articles were organized into fifteen different primary categories coupled with sub-categories, which shows where some of the past research has been focused. In addition, trends of the research were evaluated and paths for future exploration are suggested.

Os processos oxidativos avançados (POAs) têm sido apontados como alternativa eficiente para a degradação de poluentes recalcitrantes. Entre os POAs, a fotocatálise utilizando luz solar vem sendo muito estudada tendo em vista sua aplicação no tratamento de efluentes aquosos contendo pesticidas. No presente trabalho, estudou-se a degradação do herbicida amicarbazona (AMZ) por meio do processo TiO2/UV em um reator com coletores parabólicos compostos irradiados por luz solar. Os experimentos foram realizados segundo uma matriz Doehlert para o estudo da influência da concentração inicial de AMZ (20-100 mg L-1), da concentração de catalisador (0,1-1 g L-1) e do número de tubos expostos à luz solar (1-9). Amostras retiradas ao longo do tempo foram analisadas quanto às concentrações de AMZ e de carbono orgânico total (TOC). As medidas radiométricas realizadas indicaram que a radiação UVB-UVA correspondeu em média a ca. 4% da radiação solar total incidente entre 310-2800 nm; a actinometria de ferrioxalato indicou fluxo fotônico médio de 3,58×10-5 mol fótons m-2 s-1 para dias ensolarados típicos. O processo TiO2/UV mostrou-se eficiente para degradação do pesticida, que foi totalmente removido antes de 45 minutos de tratamento, para as seguintes condições: [AMZ]0=21,3 mg L-1; [TiO2]=0,5 g L-1; e 7 tubos. Contudo, nesse caso houve apenas ca. 24% de mineralização e na grande maioria dos casos os valores de TOC permaneceram praticamente constantes, o que indica a formação de sub-produtos recalcitrantes, cuja toxicidade e biodegradabilidade devem ser caracterizadas. A análise estatística dos resultados confirma os efeitos importantes da concentração inicial do pesticida e do número de tubos expostos (volume irradiado), cujo aumento permite compensar a menor incidência de radiação solar. Em alguns experimentos os resultados sugeriram que a degradação da AMZ foi favorecida pela maior concentração de TiO2. Na grande maioria dos casos os valores de ACM foram inferiores a 50 m2 kg-1, o que torna este parâmetro interessante para aumento de escala de processos fotocatalíticos irradiados por luz solar empregados no tratamento de efluentes aquosos contendo amicarbazona. / Advanced oxidative processes (AOP) have been considered as an efficient alternative for the degradation of recalcitrant pollutants. Photocatalysis using solar radiation has been studied for the treatment of wastewaters containing pesticides. In this work, the degradation of the herbicide amicarbazone (AMZ) by the TiO2/UV process was studied in a reactor equipped with compound parabolic collectors irradiated by solar light. The experiments were carried out according to a Doehlert matrix to study the effects AMZ initial concentration (20-100 mg L-1), catalyst concentration (0.1-1 g L-1), and number of tubes exposed to solar light (1-9). Samples were analyzed for AMZ and total organic carbon (TOC) concentrations. Radiometric measurements indicated that UVB-UVA radiation corresponded in average to about 4% of the solar radiation between 310-2800 nm; ferrioxalate actinometry resulted in an average photonic flux of 3.58×10-5 mol fótons m-2 s-1 for typical sunny days. The TiO2/UV process showed to be efficient for the degradation of the pesticide, which was completely removed before 45 minutes of treatment, for the following conditions: [AMZ]0=21.3 mg L-1; [TiO2]=0.5 g L-1; and 7 tubes. However, in this case only ca. 24% of mineralization was achieved, and in most cases TOC values remained practically constant, indicating the formation of recalcitrant by-products whose toxicity and biodegradility should be characterized. Statistical analysis of the results confirmed important effects of pesticide initial concentration and number of tubes exposed (irradiated volume), whose increase enables to compensate the lower incidence of solar radiation. Some experimental results suggested that AMZ degradation was favored by higher TiO2 concentrations. In most cases the values of ACM were lower than 50 m2 kg-1, in such a way that this parameter is interesting for scale-up of solar irradiated photocalytic processes used in the treatment of amicarbazone-containing wastewaters.

A presença de antibióticos no meio ambiente aquático tem causado crescente preocupação mundial. Além dos relatos de resistência de bactérias a antibióticos, essa classe de fármacos também pode causar efeitos tóxicos e atuar como perturbadores endócrinos em diversos organismos vivos e, possivelmente, em humanos. Dentre os antibióticos comumente usados destacam-se as sulfonamidas, detectadas em águas subterrâneas e superficiais. Os processos avançados de oxidação (POA) têm sido apontados como tecnologias eficientes para tratamento de poluentes recalcitrantes em diferentes matrizes aquosas. Dentre os POA, o processo foto-Fenton é uma alternativa para a degradação de compostos não biodegradáveis, incluindo fármacos. Uma vez que a principal limitação do processo é o intervalo de pH (2,5- 4,0), a reação pode ser vantajosamente conduzida empregando-se substâncias bio-orgânicas solúveis (BOS) como agentes complexantes de Fe3+ em condições ligeiramente ácidas (pH 5). Por sua vez, o emprego da energia ultrassônica tem sido menos estudado. Nesse contexto, o objetivo deste trabalho é estudar a degradação do antibiótico sulfadiazina (SDZ) por meio do processo foto-Fenton na presença de substâncias bio-orgânicas solúveis (UVvis/ Fe3+/H2O2/BOS) e do processo de cavitação por meio de ultrassom (US). Os resultados obtidos mostram que a sulfadiazina é eficientemente degradada por ultrassom de alta frequência. As maiores porcentagens e taxas de remoção são obtidas usando menor frequência de operação (580 kHz), maior potência dissipada e em pH ligeiramente ácido (melhor condição: pH 5,5). Além disso, a reação de Fenton, combinada com o tratamento US, melhorou notavelmente a degradação da SDZ, particularmente quando quantidades extras de H2O2 foram adicionadas ao sistema. Por sua vez, o uso de BOS como aditivos no processo foto-Fenton apresenta influência marcante na fotodegradação da SDZ em condições ligeiramente ácidas (pH 5). Os BOS podem estabilizar espécies de ferro em solução aquosa em pH próximos ao neutro, o que constitui uma propriedade de grande interesse. Sob as condições estudadas, o BOS CVT230 foi mais eficiente do que FORSUD, provavelmente devido às diferenças nos grupos funcionais presentes na composição destas substâncias. Finalmente, foram calculados os indicadores de consumo de energia elétrica por ordem de grandeza (EEO) para o processo de ultrassom (1572 kW h m-3 ordem-1) e área do coletor por ordem de grandeza (ACO) para o processo foto-Fenton (8,07 m2 m-3 ordem-1). / The potential impacts of antibiotic residues in the environment have become an emerging concern during recent years due to their relation with the development of resistant bacteria, and in some cases to their ability to cause toxic and endocrine disrupting effects in humans and other living organisms. Highlighted among the commonly used antibiotics are the sulfonamides, detected in groundwater and surface water. Advanced oxidation processes (AOP) might constitute an important alternative to deal with pharmaceuticals degradation. Among them, the photo-Fenton process has been widely used. One of its major drawbacks is the highly acidic pH needed (2,5-4,0) to avoid the formation of photochemically inactive iron oxides and hydroxides. The ability of soluble bio-organic substances (SBO) to complex metal cations such as iron is useful for the development of photo-Fenton at mild acidic conditions (pH 5). In turn, the use of ultrasonic energy has been less studied. In this context, the aim of this work is to study the degradation of the antibiotic sulfadiazine (SDZ) by the photo-Fenton process in the presence of soluble bio-organic substances (UV-vis/Fe3+/H2O2/SBO) and by ultrasonic cavitation (US). The results confirm that SDZ is effectively degraded by highfrequency ultrasound. Higher SDZ percent removals and removal rates were observed for the lowest operating frequency (580 kHz), higher dissipated power, and in slightly acidic solution (pH 5.5). On the other hand, SDZ degradation is highly improved in the case of the US/ Fe(II)/H2O2 system. The use of the SBO as Fenton additives in turn has a remarkable influence in SDZ photodegradation at slightly acid conditions (pH 5). This could be ascertained to the complexation of iron by the SBO, hence maintained in the reaction medium as a photoactive species. Under the studied conditions, the BOS CVT230 was more efficient than FORSUD, probably due to differences in the functional groups present in the composition of these substances. Finally, the figures-of merit electrical energy per order (EEO) and collector area per order (ACO) were calculated for the ultrasound (1572 kW h m-3 ordem-1) and photo-Fenton (8,07 m2 m-3 ordem-1) processes respectively.

Im Rahmen der vorliegenden Arbeit wurden zwei verschiedene Klassen oxidischer Nanomaterialien nasschemisch synthetisiert und strukturell-morphologisch charakterisiert. Zum einen betrifft dies TiO2-, TiO2/SiO2-, Ag/TiO2- und Pd/TiO2-Sole, welche die photokatalytisch aktive Modifikation Anatas in nanokristalliner Form enthalten und über einen solvothermalen Sol-Gel-Prozess hergestellt werden konnten. Im Hinblick auf eine potentielle Anwendung in der Desinfektionstechnologie und für den Abbau organischer Umweltschadstoffe wurde die photokatalytische Aktivität von Pulvern und Beschichtungen auf Textil durch E. coli-Abtötung bzw. Modellfarbstoffabbau untersucht. Im Weiteren wurde die antimikrobielle Aktivität pyroelektrischer LiNbO3- und LiTaO3-Pulvermaterialien unter zyklischer thermischer Anregung nachgewiesen. Diese als Pyroelektrokatalyse bezeichnete Nutzung des pyroelektrischen Effektes in einem katalytischen bzw. elektrochemischen Prozess ist dabei von grundlegender Neuheit. Aufsetzend auf den physiko-chemischen Grundlagen dieses Phänomens wurde eine Hypothese des Mechanismus entwickelt und in Analogie zur Photokatalyse diskutiert. / This thesis deals with two classes of oxidic nanomaterials that were synthesized by chemical solution routes and characterized with respect to structure and morphology. Sols of TiO2, TiO2/SiO2, Ag/TiO2 and Pd/TiO2 containing the photocatalytically active modification anatase in nanocrystalline form were prepared via a solvothermal sol-gel process. With regard to potential application in disinfection and environmental remediation technology the photocatalytic activity of powders and coatings on textile was investigated by means of E. coli decomposition and organic dye degradation. Further the antimicrobial activity of pyroelectric LiNbO3 and LiTaO3 powder materials under cyclical thermal excitation was demonstrated. In this context the application of the pyroelectric effect in a catalytic or electrochemical process – termed as pyroelectrocatalysis – is of fundamental novelty. Based on the physico-chemical principles of the phenomenon a hypothesis of the mechanism was developed and discussed in analogy with photocatalysis.

Ocean optical studies have been conducted extensively in open ocean waters but less so in coastal waters where the influence of human population is increasing dramatically. The waters of the Strait of Georgia, British Columbia, Canada, are very important to the rearing of young salmon and herring, and to the fishing industry of British Columbia overall. The oceanography and plankton communities of the Strait have been researched extensively, however the forces behind the frequent occurrence of phytoplankton blooms in these waters still causes debate among researchers. In order to shed some light onto this topic and increase our knowledge of the characteristics of the waters of the Strait of Georgia, optical and bio-physical data were measured in the euphotic waters of the Strait in late spring and early summer of 2006. Hyperspectral optical data were measured for the first time in these waters using in situ optical profilers to collect inherent optical properties and radiometric quantities that were later used to derive apparent optical properties. The inherent optical properties included absorption coefficient, spectral beam attenuation coefficient, chromophoric dissolved organic matter absorption coefficient, particulate absorption coefficient, and particulate scattering coefficient. In situ irradiances and radiances were used to derive various diffuse attenuation coefficients. Water masses in the euphotic zone of the Strait of Georgia were then classified into three optical water masses according to their inherent optical properties using a clustering algorithm. OM1 waters were characterized by high and spectrally-invariant particulate scattering due to inorganic particles carried by the Fraser River plume. Absorption and scattering showed some spectral dependence in OM2 waters, with particles and chromophoric dissolved organic matter contributing equally to light absorption. The deepest waters, OM3, were the least influenced by the Fraser River, and the contribution of chromophoric dissolved organic matter to absorption was greater than in OM1 and OM2. A radiative transfer model, Hydrolight, was used to model some of the optical properties that were not collected in situ and then used to assess the magnitude of light available to phytoplankton in the Strait. Based on the minimum light requirements for photosynthesis of two of the main phytoplankton species in the Strait, the analysis presented here showed that there was enough light available for photosynthesis in the photosynthetically-available radiation range for the two phytoplankton species in all three optical water masses.

Made available in DSpace on 2014-12-17T15:48:06Z (GMT). No. of bitstreams: 1 SergioQM.pdf: 363127 bytes, checksum: 7b8fb995a67b3e514e8b774e59124df3 (MD5) Previous issue date: 2006-03-03 / New programming language paradigms have commonly been tested and eventually incorporated into hardware description languages. Recently, aspect-oriented programming (AOP) has shown successful in improving the modularity of object-oriented and structured languages such Java, C++ and C. Thus, one can expect that, using AOP, one can improve the understanding of the hardware systems under design, as well as make its components more reusable and easier to maintain. We apply AOP in applications developed using the SystemC library. Several examples will be presented illustrating how to combine AOP and SystemC. During the presentation of these examples, the benefits of this new approach will also be discussed / Novos paradigmas de linguagens de programa??o v?em sendo comumente testados e geralmente s?o incorporados depois por linguagens de descri??o de hardware. Recentemente, a programa??o orientada a aspectos (POA) provou ser ?til na tentativa de melhorar a modularidade de linguagens estruturadas e orientadas a objeto tais como Java, C++ e C. Diante de tal fato, podemos esperar que o uso de POA pode melhorar o entendimento de sistemas hardware que est?o sendo projetados, bem como tornar seus componentes mais reus?veis e f?ceis de manter. Iremos abordar ent?o o uso de POA em aplica??es desenvolvidas utilizando a biblioteca SystemC. Ser?o apresentados v?rios exemplos que ilustram o uso de POA juntamente com SystemC, mostrando alternativas e discutindo os seus benef?cios

Os processos oxidativos avançados (POAs) têm sido apontados como alternativa eficiente para a degradação de poluentes recalcitrantes. Entre os POAs, a fotocatálise utilizando luz solar vem sendo muito estudada tendo em vista sua aplicação no tratamento de efluentes aquosos contendo pesticidas. No presente trabalho, estudou-se a degradação do herbicida amicarbazona (AMZ) por meio do processo TiO2/UV em um reator com coletores parabólicos compostos irradiados por luz solar. Os experimentos foram realizados segundo uma matriz Doehlert para o estudo da influência da concentração inicial de AMZ (20-100 mg L-1), da concentração de catalisador (0,1-1 g L-1) e do número de tubos expostos à luz solar (1-9). Amostras retiradas ao longo do tempo foram analisadas quanto às concentrações de AMZ e de carbono orgânico total (TOC). As medidas radiométricas realizadas indicaram que a radiação UVB-UVA correspondeu em média a ca. 4% da radiação solar total incidente entre 310-2800 nm; a actinometria de ferrioxalato indicou fluxo fotônico médio de 3,58×10-5 mol fótons m-2 s-1 para dias ensolarados típicos. O processo TiO2/UV mostrou-se eficiente para degradação do pesticida, que foi totalmente removido antes de 45 minutos de tratamento, para as seguintes condições: [AMZ]0=21,3 mg L-1; [TiO2]=0,5 g L-1; e 7 tubos. Contudo, nesse caso houve apenas ca. 24% de mineralização e na grande maioria dos casos os valores de TOC permaneceram praticamente constantes, o que indica a formação de sub-produtos recalcitrantes, cuja toxicidade e biodegradabilidade devem ser caracterizadas. A análise estatística dos resultados confirma os efeitos importantes da concentração inicial do pesticida e do número de tubos expostos (volume irradiado), cujo aumento permite compensar a menor incidência de radiação solar. Em alguns experimentos os resultados sugeriram que a degradação da AMZ foi favorecida pela maior concentração de TiO2. Na grande maioria dos casos os valores de ACM foram inferiores a 50 m2 kg-1, o que torna este parâmetro interessante para aumento de escala de processos fotocatalíticos irradiados por luz solar empregados no tratamento de efluentes aquosos contendo amicarbazona. / Advanced oxidative processes (AOP) have been considered as an efficient alternative for the degradation of recalcitrant pollutants. Photocatalysis using solar radiation has been studied for the treatment of wastewaters containing pesticides. In this work, the degradation of the herbicide amicarbazone (AMZ) by the TiO2/UV process was studied in a reactor equipped with compound parabolic collectors irradiated by solar light. The experiments were carried out according to a Doehlert matrix to study the effects AMZ initial concentration (20-100 mg L-1), catalyst concentration (0.1-1 g L-1), and number of tubes exposed to solar light (1-9). Samples were analyzed for AMZ and total organic carbon (TOC) concentrations. Radiometric measurements indicated that UVB-UVA radiation corresponded in average to about 4% of the solar radiation between 310-2800 nm; ferrioxalate actinometry resulted in an average photonic flux of 3.58×10-5 mol fótons m-2 s-1 for typical sunny days. The TiO2/UV process showed to be efficient for the degradation of the pesticide, which was completely removed before 45 minutes of treatment, for the following conditions: [AMZ]0=21.3 mg L-1; [TiO2]=0.5 g L-1; and 7 tubes. However, in this case only ca. 24% of mineralization was achieved, and in most cases TOC values remained practically constant, indicating the formation of recalcitrant by-products whose toxicity and biodegradility should be characterized. Statistical analysis of the results confirmed important effects of pesticide initial concentration and number of tubes exposed (irradiated volume), whose increase enables to compensate the lower incidence of solar radiation. Some experimental results suggested that AMZ degradation was favored by higher TiO2 concentrations. In most cases the values of ACM were lower than 50 m2 kg-1, in such a way that this parameter is interesting for scale-up of solar irradiated photocalytic processes used in the treatment of amicarbazone-containing wastewaters.

A presença de antibióticos no meio ambiente aquático tem causado crescente preocupação mundial. Além dos relatos de resistência de bactérias a antibióticos, essa classe de fármacos também pode causar efeitos tóxicos e atuar como perturbadores endócrinos em diversos organismos vivos e, possivelmente, em humanos. Dentre os antibióticos comumente usados destacam-se as sulfonamidas, detectadas em águas subterrâneas e superficiais. Os processos avançados de oxidação (POA) têm sido apontados como tecnologias eficientes para tratamento de poluentes recalcitrantes em diferentes matrizes aquosas. Dentre os POA, o processo foto-Fenton é uma alternativa para a degradação de compostos não biodegradáveis, incluindo fármacos. Uma vez que a principal limitação do processo é o intervalo de pH (2,5- 4,0), a reação pode ser vantajosamente conduzida empregando-se substâncias bio-orgânicas solúveis (BOS) como agentes complexantes de Fe3+ em condições ligeiramente ácidas (pH 5). Por sua vez, o emprego da energia ultrassônica tem sido menos estudado. Nesse contexto, o objetivo deste trabalho é estudar a degradação do antibiótico sulfadiazina (SDZ) por meio do processo foto-Fenton na presença de substâncias bio-orgânicas solúveis (UVvis/ Fe3+/H2O2/BOS) e do processo de cavitação por meio de ultrassom (US). Os resultados obtidos mostram que a sulfadiazina é eficientemente degradada por ultrassom de alta frequência. As maiores porcentagens e taxas de remoção são obtidas usando menor frequência de operação (580 kHz), maior potência dissipada e em pH ligeiramente ácido (melhor condição: pH 5,5). Além disso, a reação de Fenton, combinada com o tratamento US, melhorou notavelmente a degradação da SDZ, particularmente quando quantidades extras de H2O2 foram adicionadas ao sistema. Por sua vez, o uso de BOS como aditivos no processo foto-Fenton apresenta influência marcante na fotodegradação da SDZ em condições ligeiramente ácidas (pH 5). Os BOS podem estabilizar espécies de ferro em solução aquosa em pH próximos ao neutro, o que constitui uma propriedade de grande interesse. Sob as condições estudadas, o BOS CVT230 foi mais eficiente do que FORSUD, provavelmente devido às diferenças nos grupos funcionais presentes na composição destas substâncias. Finalmente, foram calculados os indicadores de consumo de energia elétrica por ordem de grandeza (EEO) para o processo de ultrassom (1572 kW h m-3 ordem-1) e área do coletor por ordem de grandeza (ACO) para o processo foto-Fenton (8,07 m2 m-3 ordem-1). / The potential impacts of antibiotic residues in the environment have become an emerging concern during recent years due to their relation with the development of resistant bacteria, and in some cases to their ability to cause toxic and endocrine disrupting effects in humans and other living organisms. Highlighted among the commonly used antibiotics are the sulfonamides, detected in groundwater and surface water. Advanced oxidation processes (AOP) might constitute an important alternative to deal with pharmaceuticals degradation. Among them, the photo-Fenton process has been widely used. One of its major drawbacks is the highly acidic pH needed (2,5-4,0) to avoid the formation of photochemically inactive iron oxides and hydroxides. The ability of soluble bio-organic substances (SBO) to complex metal cations such as iron is useful for the development of photo-Fenton at mild acidic conditions (pH 5). In turn, the use of ultrasonic energy has been less studied. In this context, the aim of this work is to study the degradation of the antibiotic sulfadiazine (SDZ) by the photo-Fenton process in the presence of soluble bio-organic substances (UV-vis/Fe3+/H2O2/SBO) and by ultrasonic cavitation (US). The results confirm that SDZ is effectively degraded by highfrequency ultrasound. Higher SDZ percent removals and removal rates were observed for the lowest operating frequency (580 kHz), higher dissipated power, and in slightly acidic solution (pH 5.5). On the other hand, SDZ degradation is highly improved in the case of the US/ Fe(II)/H2O2 system. The use of the SBO as Fenton additives in turn has a remarkable influence in SDZ photodegradation at slightly acid conditions (pH 5). This could be ascertained to the complexation of iron by the SBO, hence maintained in the reaction medium as a photoactive species. Under the studied conditions, the BOS CVT230 was more efficient than FORSUD, probably due to differences in the functional groups present in the composition of these substances. Finally, the figures-of merit electrical energy per order (EEO) and collector area per order (ACO) were calculated for the ultrasound (1572 kW h m-3 ordem-1) and photo-Fenton (8,07 m2 m-3 ordem-1) processes respectively.