The aim of this work is to test the proposed approach of algal scavenging as a driver of sediment mercury (Hg) on different time scales and to gain a better understanding of the mechanisms of Hg accumulation in lake sediments. A 3000-year sediment record from Nylandssjön in northern Sweden was analysed for this purpose, as well as a 20-year sediment record from the seasonal sediment traps of this lake. The diatom proxy biogenic silica (bSi) was determined by Fourier transform infrared spectroscopy (FTIRS) and chlorophyll-a (Chl-a) as a proxy for primary productivity by non-destructive visible near-infrared reflectance spectroscopy (VNIRS). Silica, normalised to minerogenic matter by aluminium (Si/Al) as an indirect diatom proxy and other geochemical parameters were analysed by the non-destructive method of X-ray fluorescence spectroscopy (XRF). The Hg content in the sediment was determined using the the thermal decomposition atomic absorption spectrophotometers (TD-AAS) method. Over the different time scales, organic matter (OM) is an important control factor for Hg, which in turn was strongly associated with primary productivity. Hg was normalised against OM by determining the Hg/LOI or Hg/C ratios. No positive correlation was found between the normalised Hg ratios and the proxies of primary productivity (bSi, Chl-a and Si/Al). Negative correlations between OM and minerogenic elements coinciding with human-induced erosion events and increasing Hg levels in the sediment were found. This is true, both for the long-term record in the sediment cores and the high-resolution data from the sediment traps. Furthermore, in the seasonal sediment record of the sediment traps, in-lake processes like lake turnover in spring and autumn could be linked to precipitation of iron oxyhydroxides (FeOOH) and increasing sedimentary Hg. This may be supported by the parallel sediment accumulation of other metals like nickel (Ni) and zinc (Zn) at the time of the lake turnover.

No description available.

No / Vitiligo is characterized by a progressive loss of inherited skin color. The cause of the disease is still unknown. To date, there is accumulating in vivo and in vitro evidence for massive oxidative stress via hydrogen peroxide (H2O2) and peroxynitrite (ONOO−) in the skin of affected individuals. Autoimmune etiology is the favored theory. Since depletion of the essential amino acid l-tryptophan (Trp) affects immune response mechanisms, we here looked at epidermal Trp metabolism via tryptophan hydroxylase (TPH) with its downstream cascade, including serotonin and melatonin. Our in situ immunofluorescence and Western blot data reveal significantly lower TPH1 expression in patients with vitiligo. Expression is also low in melanocytes and keratinocytes under in vitro conditions. Although in vivo Fourier transform-Raman spectroscopy proves the presence of 5-hydroxytryptophan, epidermal TPH activity is completely absent. Regulation of TPH via microphthalmia-associated transcription factor and l-type calcium channels is severely affected. Moreover, dopa decarboxylase (DDC) expression is significantly lower, in association with decreased serotonin and melatonin levels. Computer simulation supports H2O2/ONOO−-mediated oxidation/nitration of TPH1 and DDC, affecting, in turn, enzyme functionality. Taken together, our data point to depletion of epidermal Trp by Fenton chemistry and exclude melatonin as a relevant contributor to epidermal redox balance and immune response in vitiligo.

No description available.

Les particules d’aérosol sont une composante essentielle de l’atmosphère, et cette importance s’amplifie lors d’une éventuelle libération dans l’atmosphère de matières radioactives sous forme particulaire. En effet, pour améliorer la connaissance autour de la contamination des sols consécutive à une émission de particules, il est important d’étudier le rabattement des particules par la pluie sous le nuage. Dans ce but, des expériences sont menées à l’échelle microphysique (expérience BERGAME) pour quantifier l’efficacité des gouttes de pluie à collecter les particules. Ceci permet au final d’améliorer la modélisation du lessivage des aérosols atmosphériques par la pluie à méso-échelle. Le modèle utilisé est DESCAM qui décrit de manière détaillée les distributions granulométriques en masse et en nombre des particules pour chaque type d’aérosol et des hydrométéores et calcule leur évolution due aux processus microphysiques nuageux. L’expérience BERGAME a été dimensionnée et construite pour mesurer l’efficacité de collecte car les mesures de ce paramètre se sont avérées en désaccord avec les modèles classiques de la littérature pour les gouttes de pluie d’un diamètre supérieur au millimètre. Un montage optique a été imaginé pour tenter de comprendre quels mécanismes de collecte sont négligés dans les modèles standards. Un nouveau modèle d’efficacité de collecte pour les gouttes d’un diamètre de 2 mm est alors proposé prenant en compte pour les grosses gouttes une recirculation turbulente dans le sillage de la goutte capable d’augmenter de façon importante la capture des petites particules. Les nouvelles efficacités de collecte ainsi mesurées et paramétrées sont ajoutées au modèle de nuage DESCAM. Des modifications significatives sur la modélisation du lessivage par DESCAM sont observées, ouvrant ainsi la voie à une amélioration de la modélisation de la contamination des sols par les modèles de dispersion atmosphérique. / Aerosol particles are an important component of the atmosphere and are of great concern in the case of an accidental release of radioactive particles. To better understand ground contamination due to a particle release in the vicinity of an accident, it is important to study the particle scavenging associated with rain. To achieve this objective during this thesis, an experiment at the microphysical scale (BERGAME experiment) was developed and the modelling of the washout was improved at mesoscale. The model used was DESCAM : a microphysics model that describes the bin size distributions for aerosol particles and hydrometeors and calculates their evolution due to microphysical cloud processes. The BERGAME experiment was designed and built to measure the collection efficiencies which disagree with theoretical calculation. Using an optical method, it was shown that those discrepancies were due to rear capture. A new model of collection efficiencies for the 2 mm drops was proposed that takes into account for big raindrops the turbulent circulation occurring downstream increasing significantly the capture of small particles. The corrected collection efficiencies were implemented in the DESCAM model. By this way, significant modifications of the modelling were observed and studied. This is an important step toward an accurate modelling of the ground contamination in atmospheric dispersion models.

The eco-epidemiology of bovine tuberculosis (Tb) in wild deer (mainly red deer Cervus elaphus) in New Zealand was investigated. Bovine Tb is caused by Mycobacterium bovis. Specific aims were to clarify the likely routes of infection in deer, and to determine the status of deer as hosts of Tb, the likely rates and routes of inter- and intra-species transmission between deer and other wildlife hosts, the role of deer in spreading Tb, and the likely utility of deer as sentinels of Tb presence in wildlife. As the possum (Trichosurus vulpecula) is the main wildlife host of Tb, the research also included some investigation of transmission routes in possums. Patterns of infection were measured in 994 deer killed between 1993 and 2003. Tb prevalence varied between areas (range 8–36%). Few deer had generalised infection, with 21–68% of infected deer having no visible lesions, depending on the area. The retropharyngeal lymph nodes and oropharyngeal tonsils were commonly infected. No dependent fawns less than 0.75 years old were infected, indicating intra-species transmission is rare in wild deer. Where possums were not controlled, the net (cumulative) force of infection in young (1–4 y) deer was 0.10–0.24 per year in males and 0.09–0.12 per year in females, but much lower in older deer (less than 0.05 per year). Possum control reduced the net force of infection quickly, and eventually to zero. However, Tb persisted in possum-controlled areas through immigration of infected deer and, for almost a decade, through the survival of resident deer infected before possum control. Tb was lost from infected deer at an exponential rate of 0.13 per year, mostly as a result of deer recovering from infection rather than dying from it. Wild deer do die of Tb, but there was no discernible effect on age structure. The occurrence of infection in deer was not linked to the local deer or possum density at their kill sites (i.e. in their home range), but the area-wide prevalence of Tb in deer was closely correlated with Tb levels in possums, which were in turn correlated with area-wide measures of possum density. For wild deer in New Zealand, Tb is a persistent but usually inconsequential disease of the lymphatic system. It is acquired mainly by young independent deer, usually orally via the tonsils, and probably as a result of licking infected possums. Many species fed on deer carrion, including possums. Most possums encountering carrion did not feed on it, but a few fed for long periods. Other scavengers such ferrets (Mustela furo), hawks (Circus approximans), and weka (a hen-sized flightless native bird; Gallirallus australis) fed in a way that probably increased the infectivity of carrion to possums. Commercial deer hunting may have facilitated the historical establishment of Tb in possums. Scavenging (including cannibalism) and interactions with dead and dying possums are identified for the first time as potentially important routes for transmission of Tb to possums, and I develop new hypotheses involving peri- and post-mortem transmission in possums that explain many of the epidemiological patterns that are characteristic of the disease in possum. In continuous native forest, deer home range size averaged 250 hectares for six young females, and over twice that for two males. Over 90% of infected deer are likely to die within 2 km (females) or 6 km (males) of where they acquired Tb, but deer could occasionally carry Tb up to 30 km. Deer will be useful as sentinels, but only where other sentinels are rare, because the force of infection for a deer with a single infected possum in its home range is only 0.004 per year, compared to greater than 0.2 per year for deliberately released pigs. Deer are occasionally capable of initiating new cycles of infection in wildlife, but deer control is not essential to eradicate Tb from wildlife.

<p>Traumatic brain injury (TBI) is a leading cause of death and disability TBI survivors often suffer from severe disturbances of cognition, memory and emotions. Improving the treatment is of great importance, but as of yet no specific neuroprotective treatment has been found. After TBI there are changes in ion homeostasis and protein regulation, causing generation of reactive oxygen species (ROS). Overproduction of ROS can lead to damage cellmembranes, proteins and DNA and secondary cell death. In the present thesis experimental TBI in rats were used to study the effects of the ROS scavengers α-phenyl-N-tert-butyl-nitrone (PBN) and 2-sulfophenyl-N-tert-butyl-nitrone (S-PBN) on morphology, function, intracellular signalling and apoptosis. </p><p>Posttreatment with PBN and S-PBN resulted in attenuation of tissue loss after TBI and S-PBN improved cognitive function evaluated in the Morris water maze (MWM). Pretreatment with PBN protected hippocampal morphology, which correlated to better MWM-performance after TBI.</p><p>To detect ROS-generation in vivo, a method using 4-hydroxybenzoic acid (4-HBA) microdialysis in the injured cortex was refined. 4-HBA reacts with ROS to form 3,4-DHBA, which can be quantified using HPLC, revealing that ROS-formation was increased for 90 minutes after TBI. It was possible to attenuate the formation significantly with PBN and S-PBN treatment. </p><p>The activation of extracellular signal-regulated kinase (ERK) is generally considered beneficial for cell survival. However, persistent ERK activation was found in the injured cortex after TBI, coinciding with apoptosis-like cell death 24 h after injury. Pretreatment with the MEK-inhibitor U0126 and S-PBN significantly decreased ERK activation and reduced apoptosis-like cell death. Posttreatment with U0126 or S-PBN showed robust protection of cortical tissue.</p><p>To conclude: ROS-mediated mechanisms play an important role in secondary cell death following TBI. The observed effects of ROS in intracellular signalling may be important for defining new targets for neuroprotective intervention.</p>

Traumatic brain injury (TBI) is a leading cause of death and disability TBI survivors often suffer from severe disturbances of cognition, memory and emotions. Improving the treatment is of great importance, but as of yet no specific neuroprotective treatment has been found. After TBI there are changes in ion homeostasis and protein regulation, causing generation of reactive oxygen species (ROS). Overproduction of ROS can lead to damage cellmembranes, proteins and DNA and secondary cell death. In the present thesis experimental TBI in rats were used to study the effects of the ROS scavengers α-phenyl-N-tert-butyl-nitrone (PBN) and 2-sulfophenyl-N-tert-butyl-nitrone (S-PBN) on morphology, function, intracellular signalling and apoptosis. Posttreatment with PBN and S-PBN resulted in attenuation of tissue loss after TBI and S-PBN improved cognitive function evaluated in the Morris water maze (MWM). Pretreatment with PBN protected hippocampal morphology, which correlated to better MWM-performance after TBI. To detect ROS-generation in vivo, a method using 4-hydroxybenzoic acid (4-HBA) microdialysis in the injured cortex was refined. 4-HBA reacts with ROS to form 3,4-DHBA, which can be quantified using HPLC, revealing that ROS-formation was increased for 90 minutes after TBI. It was possible to attenuate the formation significantly with PBN and S-PBN treatment. The activation of extracellular signal-regulated kinase (ERK) is generally considered beneficial for cell survival. However, persistent ERK activation was found in the injured cortex after TBI, coinciding with apoptosis-like cell death 24 h after injury. Pretreatment with the MEK-inhibitor U0126 and S-PBN significantly decreased ERK activation and reduced apoptosis-like cell death. Posttreatment with U0126 or S-PBN showed robust protection of cortical tissue. To conclude: ROS-mediated mechanisms play an important role in secondary cell death following TBI. The observed effects of ROS in intracellular signalling may be important for defining new targets for neuroprotective intervention.

Lors du projet Kerguelen Ocean and Plateau compared Study (KEOPS), la dynamique des particules (vitesses de chute, temps de résidence) et les interactions entre dissous et particules (" boundary scavenging ") ont été étudiées afin de mieux comprendre les mécanismes responsables de la fertilisation naturelle en fer observée sur le plateau des Kerguelen. <br />Notre étude utilise deux radionucléides le 230Th et le 231Pa - tous deux produits de désintégration de l'uranium et très réactifs vis-à-vis des particules - comme traceurs de la dynamique des particules.<br />L'étude des vitesses de chute des particules, estimées à partir des distributions de 230Th a montré que, paradoxalement à son fort export de C, le plateau avait des vitesses de chute des particules plus faibles (S= 500 m.an-1) que les stations du large dans les eaux HNLC (S=800 m.an-1). Ce résultat, assez surprenant, soulève une question quant à la limitation du modèle de scavenging 1D dans le cadre de l'étude de la dynamique des particules des systèmes côte-large et suggère l'utilisation d'un modèle 2D pour reproduire le scavenging de ces régions.<br />Sur le plateau, les fortes concentrations de 231Pa dissous suggèrent que du 231Pa a été relâché lors de la dégradation bactérienne d'agrégats, riches en opale (phase pour laquelle le Pa a une forte affinité).<br />Sur l'escarpement à l'Est du plateau, la diminution des concentrations de 230Th et de 231Pa dissous, concomitante à l'augmentation de leur concentration dans les particules, a montré un intense boundary scavenging le long de la pente du plateau, sous l'effet de couches néphéloïdes ou de re-suspension depuis les sédiments, riches en opale.

Notre étude s’inscrit dans un processus de recherche de nouveaux composés d’origine naturelle à activités biologiques avérées à partir de macroalgues brunes, avec d’éventuelles perspectives d’exploitation industrielle. Ainsi, dans un premier volet nous avons testé des méthodologies innovantes en matière d‘extraction en utilisant trois espèces d’algues brunes comme modèles. Nous avons optimisé le protocole d’extraction solide/liquide en estimant divers paramètres cruciaux qui influent sur le rendement d’extraction et sur les activités antiradicalaires des composés extraits. Soucieux de trouver une méthodologie innovante d’extraction plus « verte » répondant aux normes européennes, nous avons donc testé des méthodes d’extraction utilisant des solvants dans leur état supercritique ou sous forme pressurisés. La comparaison avec le procédé d’extraction solide/liquide nous a permis de sélectionner l’extraction par fluides pressurisés (PLE) employée avec un mélange Ethanol-Eau pour l’extraction de composés antiradicalaires avec une haute efficacité. Dans une deuxième partie nous nous sommes intéressés aux variations quantitatives et qualitatives des principales macromolécules présentes chez l’espèce invasive Sargassum muticum en Europe. L’emploi de deux techniques analytiques, RMN HR-MAS et spectroscopie IR, nous a permis d’avoir une vue d’ensemble des compartiments susceptibles de subir des variations selon la position géographique d’une même espèce à large répartition. Cette étude nous a montré comment une espèce est capable de changer sa composition biochimique en fonction de son environnement et ainsi s’acclimater à des milieux assez différents. Ce travail a mis en évidence les effets de différents paramètres environnementaux sur les compartiments lipidique (analysés en GC), protéique ainsi que sur les quantités de carbohydrates et de pigments (analysés en HPLC). L’influence de ces paramètres sur la taille des individus de Sargassum muticum a également été discutée. La dernière partie de cette étude nous a permis de décrire les variations quantitatives et qualitatives des phlorotannins chez l’espèce invasive Sargassum muticum sur une grande échelle spatiale, le long d’un gradient latitudinal (Norvège-Portugal). Dans un premier temps cette variabilité a été appréhendée grâce à un suivi temporel et spatial des teneurs en phlorotannins. L’étude des variabilités intra-spécifiques et intra-individuelles nous a permis de mettre en évidence un effet du stade de développement et de la partie de l’algue considérée : les teneurs et activités des phlorotannins sont plus importantes dans les crampons et chez les individus matures. Après la recherche d’un protocole simple pour la semi-purification des composés phénoliques présent chez Sargassum muticum, nous avons pu mettre en évidence la présence de composés de type phlorethol au moyen de techniques de RMN à deux dimensions (2D). Ces fractions semi-purifiées possèdent des activités antiradicalaire et antibactérienne notoires. Enfin, l’utilisation de plusieurs techniques de séparation membranaires nous a permis d’estimer le poids moléculaire des différents composés présents dans le pool de composés phénoliques extrait. Enfin, suite aux constats effectués sur les populations, l’effet de l’intensité lumineuse et de la température de l’eau a pu être apprécié isolément : les radiations UVA et UVB boostent la production de CP alors qu’une augmentation de la température fait chuter la production de CP chez S. muticum. / Our study is part of the research process for new compounds of natural origin with biological activities and possible industrial perspectives. In a first part, we tested innovative extraction methodologies using three brown algae species as model. We optimized the solid/liquid extraction protocol by estimating diverse crucial parameters which influence the extraction yield and radical scavenging activities of extracts. In order to find an innovative and more "green" extraction methodology answering the European standards, we thus tested more recent extraction methods using solvents in their supercritical state or under pressure. The comparison with the solid/liquid process allowed us to select pressurized liquid extraction (PLE) using an ethanol-water mixture for the extraction of active compounds with a high efficiency, but also to select Sargassum muticum as an interesting model for further investigations. In a second part, we were interested in the quantitative and qualitative variations of the main macromolecules present in the invasive species S. muticum in Europe. The employment of two analytical techniques (NMR HR-MAS and IR spectroscopy), allowed us to have an overview of biochemical parts of the algae, which vary according to the geographical position of this wide spread species. This study showed how a species is able to modify its biochemical composition, and then to acclimate, according to the environment. We then focused on molecules, which showed important variations along the latitudinal range of S. muticum. This work highlighted the effects of environmental parameters on lipid (GC analysis) and protein compartments as well as on carbohydrates and pigments quantities (HPLC analysis). The influence of these parameters on the size of individuals was also discussed. The last part of this study allowed us to describe the quantitative and qualitative variations of phlorotannins in S. muticum on a large spatial scale, along a latitudinal gradient (Norway-Portugal). At first this variability was measured thanks to temporal and spatial follow-up of the phlorotannins contents. The study of intra-specific and intra-individual variabilities allowed us to highlight an effect of the development stage and of the seaweed part: phlorotannins contents and activities are more important in holdfast and in mature individuals. After the research of a simple protocol for the phenolic compounds semi-purification present in Sargassum muticum, we were able to highlight the presence of compounds of only phlorethol type in this species by means of 2D RMN techniques. These semi-purified fractions possess notorious radical scavenging and antibacterial activities. Finally, the use of several membrane separation techniques allowed us to consider the molecular weight of the various compounds present in the extracted pool of phenolic compounds. Finally, under controlled conditions, the effects of the light quality and the seawater temperature were tested: UV-A and UV-B radiations boost the production of CP while an increase of the temperature makes the phlorotannins production decreasing in S. muticum.