Les hydrocarbures aromatiques polycycliques (HAP) sont des composés organiques présents dans l’ensemble des compartiments environnementaux. Dans l’atmosphère, leurs sources sont à la fois naturelles (feux de biomasse, éruptions volcaniques) et anthropiques (industrie, transport, chauffage résidentiel). Une fois émis, sous forme gazeuse ou adsorbés à la surface de particules atmosphériques, les HAP sont susceptibles d’être impliqués dans des processus physico-chimiques tels que la photodégradation et/ou des réactions d’oxydation avec différentes espèces radicalaires. Du fait de leur toxicité avérée, ces composés font l’objet de différentes réglementations, législations françaises et européennes. Concernant le compartiment atmosphérique, seul le benzo(a)pyrène présente aujourd’hui des seuils d’émission à respecter. Afin de faire évoluer ces textes et de mettre en place des mesures de réduction d’émissions, diverses approches ont été développées dans le but de différencier leurs sources dans l’atmosphère. L’approche moléculaire, basée sur les profils moléculaires et les rapports de concentrations, permet d’apporter des informations quant à leurs origines. En revanche, elle souffre de biais induits par les conditions de formation des HAP (température, conditions environnementales…) et par les processus physico-chimiques dans lesquels ils sont impliqués. L’objectif principal de ce travail est de mettre en place une méthodologie de traçage de sources des HAP particulaires par une approche isotopique. Le développement du protocole analytique a été réalisé pour déterminer la composition isotopique moléculaire des HAP particulaires par GC/C/IRMS. Il a été montré que la réactivité des HAP sous l’action d’oxydants (O3, NO2, OH) et/ou de la lumière solaire n’induisait pas de variation significative de la composition isotopique moléculaire des HAP. Cette méthodologie a ainsi pu être appliquée sur des échantillons naturels, prélevés sur des sites caractérisés par des sources spécifiques. Il a été montré que les 13C/12C des HAP, en complément de données moléculaires, permettent de différencier les origines de ces composés. Par exemple, les caractéristiques moléculaires et isotopiques de HAP issus de la combustion de plusieurs espèces de bois d’origine méditerranéenne ont été déterminées en appliquant cette méthodologie à des échantillons collectés directement à l’émission. Enfin, dans le cadre de l’étude de la pollution et de ses impacts dans le Bassin d’Arcachon, les apports atmosphériques en HAP ont été mesurés par l’approche moléculaire couplée à d’autres outils (rétrotrajectoires, oxydants, roses des vents…) afin de compléter le diagnostic environnemental. / Polycyclic Aromatic Hydrocarbons (PAH) are carcinogenic compounds, present in all the compartments of the Environment. In the atmosphere, their sources are both from natural (biomass burning, volcanic emissions...) and anthropogenic (transport, industry, residential heating...) origins. Once emitted in the atmosphere, PAH are distributed between the gaseous or particulate phases and may be involved in different physico-chemical processes such as photodegradation, radical-initiated oxidations... Due to their carcinogenicity, PAH emissions are nowadays subjected to various regulations from France and more largely, European Union. In the atmosphere, benzo(a)pyrene has been selected as representative of the PAHs because of its high toxicity. In order to improve regulations involving emission reductions, several methodologies have been developed to perform source apportionment. The most commonly used in the literature is the molecular approach, based on molecular profiles and particular ratios. Nevertheless, conditions of PAH formation and physico-chemical processes affect these characteristic values. The main objective of this work was to develop a new methodology of particulate-PAH source tracking based on the molecular isotopic composition. The development of analytical procedure was performed to determine 13C/12C of PAHs by GC/C/IRMS. The study of the impact of PAH reactivity in the presence of O3, NO2, OH and/or solar radiations shows that no significant isotopic fractionation is induced on their isotopic compositions. Molecular isotopic approach was applied on natural particles, collected at different specific sites: 13C/12C of PAHs and molecular data allow differentiating particulate-PAH sources. Therefore, determinations of molecular and isotopic characteristics have been undertaken by applying this methodology on particulate-PAHs emitted during the combustion of fifteen Mediterranean woods. Finally, molecular approach coupled with different parameters (back-trajectories, oxidant concentrations, wind roses...) enables to measure the levels of PAH concentrations in the atmosphere in order to evaluate their impacts as a source of pollution in the Arcachon Bay.

ABSTRACT Collembola are known to feed on soil fungi, mycorrhizae and plant derived products. A recent study revealed that one species of Collembola, Protaphorura fimata, completely switched from decomposer to herbivore when live roots were present. The current study investigated the occurrence of diet-switching in Folsomia candida Willem. from plant detritus to live by examining its dietary preferences using stable isotope techniques. They were offering with live maize roots (C4 plant) in C3 soil, along with 15N enriched ryegrass litter and. Results demonstrated the presence of a partial diet-switch from detritus to live maize roots. Additional tests suggested that the diet-switch towards maize roots was a response to both improved food quality and greater food availability. The presence of live roots improved the body growth of F. candida and the incorporation of C from live roots into Collembola tissue suggesting

No description available.

No / The environmental contexts of the karstic hominin sites in South Africa have been established largely by means of faunal associations; taken together these data suggest a trend from relatively closed and more mesic to open, drier environments from about 3 to 1.5 Ma. Vrba argued for a major shift within this trend ca. 2.4¿2.6 Ma, an influential proposal that posited links between bovid (and hominin) radiation in Africa and the intensification of Northern Hemisphere Glaciation. Yet faunal approaches often rely on habitat and feeding preferences of modern taxa that may differ from those of their extinct predecessors. Here we explore ways of extending 13C/12C data from fossil mammals beyond denoting ¿presence¿ or ¿absence¿ of C4 grasses using the evolution of open environments in South Africa as a case study. To do so we calculated the relative proportions of C3-, mixed-, and C4-feeding herbivores for all the hominin sites for which we have sufficient data based on 13C/12C analyses of fossil tooth enamel. The results confirm a general trend towards more open environments since 3 Ma, but they also emphasize a marked change to open grassy habitats in the latest Pliocene/early Pleistocene. Mean 13C/12C for large felids also mirrored this trend.

Equine gastric glandular mucosal ulceration can have a prevalence of 58%, yet its etiology is poorly understood. In man Helicobacter pylori is the most common cause of gastritis and peptic ulcer disease. Helicobacter is uniquely able to colonize the stomach, via the action of cytoplasmic urease. Different Helicobacter species have been isolated from many mammals but none has yet been cultured from the horse. Three tests used to identify human Helicobacter infection were applied to the horse. Test 1: PCR amplification of Helicobacter specific DNA, n=12. Test 2: the Pyloritek™ rapid urease test (RUT), n=15. Test 3: the 13C-urea blood test, n=8. Gastroscopy and antral biopsy was performed in all horses. All horses demonstrated the presence of Helicobacter specific gene material by PCR. Biopsy specimens from 7/15 horses were urease positive by RUT. Significant 13C enrichment of the body CO2 pool was found in all horses after intragastric administration 13C-urea (p<0.05). As Helicobacter is currently the only known gastric urease positive microorganism, the demonstration of this activity in horses positive by PCR strongly supports the presence of an equine gastric Helicobacter species. Variations of 13C-urea blood test were further examined and a single protocol was found to be most applicable. As the horse is a hind gut fermenter, the effect of cecal urease on the test was examined by laparoscopic intracecal administration of 13C-urea. Significant cecal urease activity was demonstrated however the timing of peak 13C enrichment may limit any effect on the gastric test to 90 minutes onwards. / Master of Science

A teoria do limite de similaridade é uma teoria central para o entendimento da estruturação das comunidades ecológicas, e prevê que a coexistência de duas espécies de forma estável somente é possível caso exista um limite de semelhança entre elas. Nesse sentido, é esperado que ocorra partilha de recursos entre espécies simpátricas aparentadas como Podocnemis unifilis e Podocnemis expansa, dois quelônios amplamente distribuídos e de grande importância econômica e cultural na região amazônica. Assim, o objetivo deste estudo foi determinar os padrões de consumo de duas espécies simpátricas de quelônios, P. unifilis e P. expansa, além de verificar possíveis interações tróficas que se estabeleçam entre elas, considerando suas possíveis variações sexuais, no rio Javaés, Estado do Tocantins, Brasil. Desta forma, foram feitas análises dos conteúdos estomacais e análises isotópicas das unhas de indivíduos dessas espécies visando a determinação de suas amplitudes e sobreposições de nicho alimentar e isotópico. As sobreposições de nicho alimentar foram comparadas às sobreposições de comunidade idealizadas sem competição, por meio de modelos nulos. As sobreposições de nicho isotópico foram calculadas através de elipses bayesianas. As espécies apresentaram baixos valores de amplitude de nicho independente da medida. Entretanto, apresentaram alta sobreposição de nicho alimentar e nenhuma sobreposição de nicho isotópico. Amplitudes foram sempre reduzidas e sobreposições sempre elevadas entre os sexos. As diferenças entre as sobreposições de nicho das espécies medidas a partir das duas metodologias se relacionaram a importância de outras dimensões além da alimentar para o nicho isotópico. Os padrões de uso de recursos observados indicam que competição por alimento não está sendo relevante para a coocorrência das espécies no sistema estudado, possivelmente devido à altas disponibilidades dos recursos alimentares utilizados por P. unifilis e P. expansa. / The limiting similarity theory is a central theory for the comprehension of the structure of ecological communities, and predicts that the stable coexistence of two species is possible only if there is a limit of similarity between them. Therefore, it is expected to occur resource partitioning among sympatric related species as Podocnemis unifilis and Podocnemis expansa, two freshwater turtles widely distributed and of great economic and cultural importance in the Amazon region. The objective of this study was to determine the consumption patterns of two sympatric species of freshwater turtles, P. unifilis and P. expansa, and to identify possible trophic interactions to be established between them, considering its possible sexual variations, in the Javaés River, State of Tocantins, Brazil. Thus, were made analyzes of stomach content and isotopic analyzes of claws from individuals of these species in order to determine their amplitudes and dietary overlaps of food niche and isotopic niche. The food niche overlaps were compared with overlaps of idealized communities without competition, through null models. The isotopic niche overlaps were calculated using bayesian ellipses. The species had low niche amplitude values independent of the measure. However, the species showed high overlap of food niche and no isotopic niche overlap. Amplitudes were always reduced and overlap always high between the sexes. Differences between the niche overlaps of the species measures due the two methodologies were related to the importance of other dimensions beyond that represented by feeding to the isotopic niche. The observed patterns of resources usage indicate that competition for food is not being relevant to the co-occurrence of these species in the system studied, possibly due to the high availability of food resources used by P. unifilis and P. expansa.

Verificou-se a ocorrência dos teores totais e disponíveis de mercúrio nos sedimentos de fundo e em suspensão, e de mercúrio total em amostras de lambari (Astianax altiparanae) capturadas no ribeirão Guamium, bacia do rio Piracicaba, S.P. As concentrações foram correlacionadas aos diferentes usos dos solos limítrofes à bacia; pequena ocupação urbana com uso agrícola no distrito de Tanquinho (à montante), agrícola (médio-Guamium) e industrial (à jusante). Para tanto, foram conduzidas amostragens representativas do sedimento e da ictiofauna da bacia de drenagem nos períodos de seca e de chuva; (sedimento de fundo julho de 2008 e março de 2009) (sedimento em suspensão mar/2009); (peixes setem/2005 e fever/2006). As amostras de sedimentos de malha inferior a 0,063 mm foram solubilizadas em água-régia (3HCl + 1HNO3), as amostras de peixe foram liofilizadas e digeridas em solução nitro-sulfo-perclórica, em sistemas abertos de decomposição. A determinação de Hg nos extratos foi conduzida por espectrometria de fluorescência atômica (AFS), estando o intervalo de concentração de Hg total nos sedimentos de fundo, para o período de seca, entre 0,040 a 0,105 mg kg-1 Hg e disponível entre 0,018 e 0,064 mg kg-1. Neste mesmo substrato, para o período de chuvas, esse teor apresentou concentrações entre 0,54 a 0,13 mg kg-1 Hg e disponível de 0,010 a 0,052 mg kg-1. Em relação aos sedimentos em suspensão (época chuvosa), os teores de Hg estiveram entre 0,040 a 0,120 mg kg-1 e o disponível em 0,028 a 0,081 mg kg-1. Para a ictiofauna, cujo comprimento variou de 44 a 135 mm, o teor de Hg esteve entre 0,18 e 1,90 mg kg-1 Hg. Os valores de Hg encontrados nos substratos peixe e sedimentos (total e biodisponível) foram correlacionados com parâmetros físico-químicos do meio como, temperatura, pH, condutividade e oxigênio dissolvido da água. Para o sedimento, através dos valores de Eh e pH, construiu-se diagrama de estabilidade para o elemento mercúrio. Complementa-se a abordagem biogeoquímica do estudo, avaliando-se a influência do uso do solo no meio hídrico, através da determinação de \'delta\'13C nos sedimentos amostrados ao longo da bacia hidrográfica / There was the occurrence of total and available mercury in bottom sediments, suspended and total mercury in samples Astyanax altiparanae seizure in the river Guamium, Piracicaba river basin, SP. Concentrations were correlated to different uses land adjacent to the basin, a small urban and agricultural use, the district of Tanquinho (upstream) of the city of Piracicaba, agriculture (medium Guamium) and industrial (downstream). Representative sampling, of the sediment and the fish fauna of the drainage basin were conducted during periods of drought and rain, (bottom sediment in july 2008 and march 2009) (suspended sediment mar/2009) (fish septem/2005 and feb/2006). Samples of sediment less than 0.063 mm mesh were dissolved in 3HCl with 1HNO3, the fish samples were freeze dry and digested in solution, sulfo-nitro-perchloric, in open systems. The determination of Hg in the extracts was conducted by atomic fluorescence spectrometry (AFS), while the concentration range of total Hg in bottom sediments for the period of drought between 0.040 to 0.105 mg kg-1 Hg and available between 0,018 and 0.064 mg kg-1. In the same substrate, for the rainy season, this level showed concentrations between 0.54 to 0.13 mg kg-1 Hg and available from 0.010 to 0.052 mg kg-1. Regarding the suspended sediments (rainy season), the concentrations of Hg were between 0.040 to 0.120 mg kg-1 and available in 0.028 to 0.081 mg kg-1. For the fishes, whose length ranged 44-135 mm Hg content was between 0.18 and 1.90 mg kg-1 Hg. Values of Hg found in fish and sediment substrates (total and bioavailable), were correlated with physicochemical parameters of the medium as, temperature, pH, conductivity and dissolved oxygen from the water. For the sediment through the values of Eh and pH, was constructed diagram of stability for the element mercury. Evaluating the influence of land use on the aquatic environment, through the determination of \'delta\'13C in sediments sampled along the river basin

Les hydrocarbures aromatiques polycycliques (HAP), sont des molécules toxiques, voire cancérigènes principalement issues de la combustion incomplète de matière carbonée. De nombreux outils ont été développés afin d’identifier leurs origines et leur devenir. Cependant, ces derniers ne permettent pas toujours de parvenir à une identification précise des sources d’émissions. Une méthode prenant en compte les variations des rapports isotopiques δ 13C et δ 2H dans 16 composés a été développée et comparée à celle des ratios moléculaires. Le développement du protocole a consisté en la préparation puis la validation d’une méthode d’extraction sélective par type de matrice (eau/sédiment) et d’une méthode de purification permettant d’obtenir pour chaque molécule une résolution adaptée à leur analyse isotopique. Cette méthode a été appliquée sur divers produits de combustion franciliens ainsi que sur des échantillons de dépôts atmosphériques, d’eau et de sédiments de rivière. La mesure du δ13C et du δ2H a permis de confirmer la présence de sources locales et de caractériser les variations saisonnières de ratios. L’originalité de ce travail de recherche réside dans l’utilisation du δ2H spécifique à chaque molécule et non sur un mélange de composés. Les résultats permettent d’envisager de nouvelles perspectives sur l’utilisation des mesures isotopiques. Cette thèse représente un premier élément de réponse sur la problématique de l’emploi d’outils de traçage de molécules dans des environnements complexes. / Polyaromatic hydrocarbons (PAHs) are a group of toxic and carcinogenic organic compounds formed by petrogenic and incomplete pyrolytic processes. Although emission reductions were observed over the past 20 years, PAH contamination is still an environmental concern as these compounds are the main contaminants in the Seine watershed. Many tools were developed to identify their origins and fate. However, these methods do not always allow accurate identification of emission sources. A method integrating the variations of the isotopic ratios of δ13C and δ2H among 16 compounds was developed and compared to those of the molecular diagnostic ratio techniques. The development of the protocol consisted of the preparation and the validation of a selective extraction method by matrix type (water / sediment) and a purification step to obtain for each molecule, a resolution adapted to its isotopic analysis. That method applied to various combustion products in the Ile-de-France region, such as samples of atmospheric deposition, water and river sediments. The measurement of δ13C and δ2H signatures confirmed the presence of local sources and helped to characterize the seasonal variations of the ratios. The originality of this research work is the use of δ2H on individual PAH instead of bulk compounds. The results allow considering new perspectives for the use of isotopic measurements.

Title: The Study of Dynamic Behaviour and Interactions During the Tempera- ture-Induced Phase Separation in Polymer Solutions Author: Hana Kouřilová Department / Institute: Charles University in Prague, Faculty of Mathemat- ics and Physics, Department of Macromolecular Physics Supervisor of the doctoral thesis: doc. RNDr. Lenka Hanyková, Dr. Abstract: 1 H and 13 C high-resolution NMR spectroscopies were used for the phase separation investigation in three types of polymer solutions: i) poly(N -isopropylmethacrylamide)/D2O/ethanol with or without negatively charged comonomer sodium methacrylate, ii) random copolymers poly(N -isopro- pylmethacrylamide-co-acrylamide) in D2O, D2O/ethanol and D2O/acetone and iii) D2O solutions of polymer mixtures poly(N -isopropylmethacrylamide)/poly(N - vinylcaprolactam). For i) cononsolvency effect and influence of temperature on the phase separation was studied. Differences between mesoglobules formed as a consequence of cononsolvency effect and of temperature were found. While inside the cononsolvency-induced mesoglobules no bound ethanol molecules were detect- ed, in the mesoglobules formed by the effect of temperature ethanol molecules were present. The charge introduced into the polymer chains strenghtens polymer- solvent interactions. For ii) mesoglobules were found to be...

La maladie de Parkinson est une maladie neurodégénérative du système cerveau central conduisant à l'apparition des troubles moteurs caractéristiques de la maladie : akinésie, rigidité et tremblement de repos. La perte des neurones dopaminergiques de la voie nigro-striée va conduire à des modifications biochimiques au niveau du putamen. Notamment, les travaux réalisés en électrophysiologie, microdialyse et spectroscopie par résonance magnétique (SRM) suggèrent une hyperactivité de la voie glutamatergique cortico-striatale associée à un changement du microenvironnement glial au niveau du putamen. Ces observations conduisent à penser à une adaptation du cycle glutamate-glutamine ayant lieu entre les neurones et les astrocytes en réponse à la perte neuronale. Ainsi, dans ce travail de thèse, deux approches ont été développées afin de suivre par SRM les changement métaboliques impliqués dans la pathologie parkinsonienne, notamment les variations des concentrations en glutamate et glutamine dans le putamen. Une première approche de la quantification des métabolites cérébraux par spectroscopie du 1H, technique couramment utilisée en clinique, a été utilisée pour suivre l'évolution des métabolites d'intérêt chez des patients parkinsoniens à jeun ou suite à la prise d'un traitement dopaminergique. Si cette étude a révélé des changements de concentration en N-acetylaspartate, créatine et myoinositol chez les patiens parkinsoniens, aucun changement du métabolisme glutamatergique n'a pu être observé par cette technique, peut-être à cause d'un manque de sensibilité de la technique pour discriminer les pools de glutamate et de glutamine. De ce fait, une nouvelle approche de SRM du Carbone 13C a été développée pour le suivi du cycle glutamate-glutamine in vivo, c'est la polarisation dynamique nucléaire (PDN). Grâce à la haute sensibilité de cette technique, il est désormais possible de suivre des voies métaboliques in vivo en temps réel. La mise en place et l'optimisation de la PDN pour le suivi du cycle glutamate-glutamine a été un des objectifs au cours de ce projet de thèse. Validée sur un groupe d'animaux contrôle, cette technique offre un avenir prometteur pour l'analyse de ce flux dans les pathologies neurodégénératives. En conclusion, les stratégies diagnostiques en clinique par SRM du 1H restent, à l'heure actuelle, peu sensibles pour l'étude des modifications du cycle glutamate-glutamine in vivo chez l'homme. Les développements technologiques réalisés au cours de ce travail de thèse notamment avec la PDN du 13C laissent entrevoir une nouvelle approche pour le suivi en temps réel de ce métabolisme cérébral. Si la PDN est principalement utilisée dans des études précliniques, la disponibilité de nouveaux systèmes cliniques pourrait permettre son avènement en tant que nouvelle stratégie de diagnostic en imagerie clinique. / Parkinson's disease is a neurodegenerative disorder characterized by motor troubles such as akinesia, rigidity and tremor. The loss of dopaminergic neurons from the nigro-striatal pathway will lead to biochemical changes in the putamen. Especially, works on electrophysiology, micro dialysis and magnetic resonance spectroscopy (MRS) suggests hyperactivity of the glutamatergic cortico-striatal pathway associated with glial microenvironment changes. These observations suggest a modification of the glutamate-glutamine cycle occurring between neurons and astrocytes in response to neuronal loss.In this thesis, two approaches have been developed in order to follow by MRS the metabolic changes occuring in Parkinson's disease. In particular, we want to follow the changes in glutamate-glutamine cycle inside the putamen.in a first study, a a 1H MRS approach was used to assess the metabolic changes inside the putamen of Parkinson's disease without or under dopaminergic treatment. In this study, changes in N-acetylaspartate, creatine and myo-inositol were observed in Parkinsonian patients, but no change in glutamatergic metabolism was observed. This could be due to the lack of sensitivity of the technique to differentiate glutamate and glutamine pools.Thus, we chose to use a new 13C carbon MRS approach in order to follow dynamically in vivo the glutamate-glutamine cycle inside the brain: dynamic nuclear polarization (DNP). Thanks to the high sensitivity of this technique, it is now possible to follow metabolic pathways in vivo in real time. The implementation of DNP was assessed under a control group of animals. This technique offers a new promising tool for the analysis of this flow under pathologic conditions.To conclude, the MRS strategies for clinical diagnostic strategies remain, at present, poorly sensitive for the study of glutamate-glutamine cycle in vivo in humans. The development of DNP opens the door to a new approach for real-time monitoring of this cerebral metabolism Even if DNP is mainly used in preclinical studies at present, the development of new clinical systems could lead to its emergence as a new diagnostic strategy in clinical imaging.