<p>The European Union Water Framework Directive (WFD), with initiatives to manage surface water resources, has increased the need for fast and inexpensive methods for monitoring conditions in streams. The objective of this thesis is to assess the potential of near-infrared spectroscopy (NIRS) of epilithic material to become such method. NIRS, which is a technique that is commonly used in industry for process monitoring and quality control of products, registers the chemical properties of organic material on a molecular level. Epilithic material, i.e. the layer of dead and alive material that covers stone surfaces in streams, is continuously influenced by the stream water that flows over it, and it has the potential to integrate chemical and biological conditions over time. The temporal integration is a significant factor, since conditions in streams can change within hours or days. The thesis consists of two published papers. In the first paper a new sampler for epilithic material, the Stone Brusher, was described and the performance evaluated. The Stone Brusher is designed to take qualitative or semi-quantitative samples of epilithic material from stones at 7–50 cm water depth. The epilithic material is dislodged from the stone surface with a rotating brush enclosed in a chamber, and the material is drawn up directly into the sample bottle with an air-cylinder. The operator takes a sample quickly and without putting hands into the water. The sampler is made of plastic, stainless steel and aluminium and weighs 3.1 kg. It is designed to meet the demand for standardized sampling for research and environmental monitoring and to improve working conditions for sampling personnel. The equipment allows sampling from surfaces of bedrock and large stones that cannot be lifted from the bottom. Using data of near-infrared spectroscopy and diatom analyses, this new sampler was evaluated in comparison to the toothbrush method, a primitive method which is the current standard in EU. The results indicate that the Stone Brusher reduces sampling variability compared with the toothbrush method.</p><p>In the second paper, the Stone Brusher was used to collect epilithic material from 65 sites (42 uncontaminated and 23 contaminated) from streams in the widespread mining area called the Skellefte-district in Västerbotten, northern Sweden, in order to test the hypothesis that impact on the epilithic material caused by emissions from mining and mining-related industries can be detected using NIRS. The epilithic material was filtered onto glass fibre filters, measured by NIRS, and the results were modelled using Principal Component Analysis (PCA). The NIRS approach was evaluated by comparing it with the results of chemical and diatom analyses of the same samples. Based on PCA, the NIRS data distinguished contaminated from uncontaminated sites and performed slightly better than chemical analyses and clearly better than diatom analyses. Of the streams designated a priori as contaminated, 74 % were identified as contaminated by NIRS, 65 % by chemical analysis and 26 % by diatom analysis. Unlike chemical analyses of water or of epilithic material samples, NIRS data reflect biological impacts in the streams. Given that, and the simplicity of NIRS-analyses, further studies to assess the use of NIRS of epilithic material are justified. NIRS has the potential to become a fast method for screening in regions where large numbers of streams occur to find impacted streams or as a routine method for temporal monitoring in selected streams for early detection of environmental impact, similar to process monitoring in industry.</p>

The European Union Water Framework Directive (WFD), with initiatives to manage surface water resources, has increased the need for fast and inexpensive methods for monitoring conditions in streams. The objective of this thesis is to assess the potential of near-infrared spectroscopy (NIRS) of epilithic material to become such method. NIRS, which is a technique that is commonly used in industry for process monitoring and quality control of products, registers the chemical properties of organic material on a molecular level. Epilithic material, i.e. the layer of dead and alive material that covers stone surfaces in streams, is continuously influenced by the stream water that flows over it, and it has the potential to integrate chemical and biological conditions over time. The temporal integration is a significant factor, since conditions in streams can change within hours or days. The thesis consists of two published papers. In the first paper a new sampler for epilithic material, the Stone Brusher, was described and the performance evaluated. The Stone Brusher is designed to take qualitative or semi-quantitative samples of epilithic material from stones at 7–50 cm water depth. The epilithic material is dislodged from the stone surface with a rotating brush enclosed in a chamber, and the material is drawn up directly into the sample bottle with an air-cylinder. The operator takes a sample quickly and without putting hands into the water. The sampler is made of plastic, stainless steel and aluminium and weighs 3.1 kg. It is designed to meet the demand for standardized sampling for research and environmental monitoring and to improve working conditions for sampling personnel. The equipment allows sampling from surfaces of bedrock and large stones that cannot be lifted from the bottom. Using data of near-infrared spectroscopy and diatom analyses, this new sampler was evaluated in comparison to the toothbrush method, a primitive method which is the current standard in EU. The results indicate that the Stone Brusher reduces sampling variability compared with the toothbrush method. In the second paper, the Stone Brusher was used to collect epilithic material from 65 sites (42 uncontaminated and 23 contaminated) from streams in the widespread mining area called the Skellefte-district in Västerbotten, northern Sweden, in order to test the hypothesis that impact on the epilithic material caused by emissions from mining and mining-related industries can be detected using NIRS. The epilithic material was filtered onto glass fibre filters, measured by NIRS, and the results were modelled using Principal Component Analysis (PCA). The NIRS approach was evaluated by comparing it with the results of chemical and diatom analyses of the same samples. Based on PCA, the NIRS data distinguished contaminated from uncontaminated sites and performed slightly better than chemical analyses and clearly better than diatom analyses. Of the streams designated a priori as contaminated, 74 % were identified as contaminated by NIRS, 65 % by chemical analysis and 26 % by diatom analysis. Unlike chemical analyses of water or of epilithic material samples, NIRS data reflect biological impacts in the streams. Given that, and the simplicity of NIRS-analyses, further studies to assess the use of NIRS of epilithic material are justified. NIRS has the potential to become a fast method for screening in regions where large numbers of streams occur to find impacted streams or as a routine method for temporal monitoring in selected streams for early detection of environmental impact, similar to process monitoring in industry.

As novel engineered nanoparticles such as single-walled carbon nanotubes (SWCNT) are extensively used in nanotechnology due to their superior properties, it becomes critical to fully understand their biodistribution and effect when accidently inhaled. There fore, development of animaging technique which allow longitudinal in vivo follow-up of SWCNT effect based on their intrinsic properties is highly desirable. Non invasive free-breathing hyperpolarized 3He lung MRI protocol was developed complementary to proton systemic MR protocol to allow monitoring SWCNT based on their intrinsic iron impurities after intrapulmonary exposition. Combined toproton lung MRI and ex vivo optical and electron microscopy at different time points, this protocol represents a powerful multimodality imaging techniques which allows a full characterization of the biodistribution and biological impacts of iron containing SWCNT. SWCNT was found to produce granulomatous and inflammatory reactions in a time and dose dependent manner with their bio persistenc eafter intrapulmonary exposition.From biological impact evaluations after intrapulmonary exposition towards biomedical applications, SWCNT hold promise for applications in nanomedicine field with their distinct architecture and their novel physicochemical properties. The biodistribution and pharmacological profile of various well-dispersed pristine and functionalized SWCNT were assessed in blood and target tissues after their intra venous administration by longitudinal in vivo susceptibility weighted MRI and their potential effect on liver metabolism by ex vivo HRMAS 1H NMR. No presence ofacute toxicological effect (variation in liver metabolism) was observed confirmed by the absence of clustering in NMR spectra using Principal Component Analysis (specific biomarkers of toxicity).

Les invasions biologiques, deuxième cause de perte de biodiversité à l’échelle mondiale, représentent un risque majeur auquel nos sociétés doivent faire face. On parle d’invasion biologique lorsque des activités humaines permettent à une espèce de franchir des barrières qui jusqu’alors limitaient sa dispersion ou sa multiplication, entrainant une explosion géographique et démographique de l’espèce dans un nouvel écosystème et s’accompagnant éventuellement d’impacts économiques, sociétaux ou écologiques. La façon la plus efficace et la moins coûteuse de limiter les impacts causés par les espèces envahissante et de les prévoir en amont afin de mettre en place des mesures de prévention ciblées et efficaces et d’essayer de les éviter.L’objectif de cette thèse est de démontrer qu’il est possible d’améliorer la prédiction des invasions biologiques en développant et combinant différentes approches de modélisation de façon innovante. Les questions posées sont de savoir s’il est possible de prévoir quelles pourraient-être ces espèces, où elles pourraient devenir envahissantes et quels impacts elles pourraient avoir. Toutes les méthodes développées dans cette thèse ont été appliquées à des hyménoptères sociaux ; nombreuses espèces de fourmis (famille des Formicidés) ou frelon asiatique (famille des Vespidés, vespa Velutina nigrithorax), mais elles sont généralisables et réutilisables pour tout autre taxa.Je montre dans cette thèse qu’il est possible de développer un outil statistique de détection des espèces risquant de devenir envahissantes. J’applique cet outil aux fourmis, je fournis une liste de 15 espèces de fourmis risquant de devenir envahissantes à travers le monde et je cartographie les zones du globe risquant d’être envahies par ces espèces. Chacun des continents est menacée par au moins une de ces invasions potentielles. Dans un deuxième temps, je mets au point d’un cadre méthodologique permettant d’améliorer les prédictions d’aires de distribution des espèces en combinant leurs exigences climatiques et d’habitat, tout en respectant l’échelle géographique à laquelle ces facteurs agissent sur la distribution des espèces. J’applique cette méthode au frelon asiatique, ce qui me permet d’identifier les habitats qui lui sont les plus favorables et d’utiliser ces informations pour raffiner la prédiction de son aire favorable. En combinant le climat et l’habitat, je prédis une aire potentielle de distribution 56% plus restreinte par rapport aux estimations basées sur le climat uniquement. Enfin, dans un troisième temps, je m’intéresse au développement d’une méthode permettant de prédire spatialement les impacts causés par une invasion biologique. Pour ce faire, je prédis d’abord l’abondance potentielle du frelon asiatique en France. Je couple ensuite cette prédiction avec des données de présence de ruches et un modèle présidant l’impact du frelon asiatique sur la survie des colonies d’abeilles. J’estime enfin que cette invasion peut conduire à l’effondrement de 41% des colonies d’abeilles domestiques en France.Cette thèse met en lumière l’utilité d’intégrer la modélisation dans la construction du savoir autour des invasions biologiques, approche relativement nouvelle dans ce champ disciplinaire. De plus, elle illustre comment la modélisation et l’élaboration de prédictions peuvent aider à objectiver la prise de décision concernant la gestion des espèces envahissantes et optimiser leur efficacité en ciblant les habitats, les régions et les espèces d’action prioritaires. / Biologicals invasions, the second cause of biodiversity loss worldwide, represent a major threat that our societies have to face. Invasive species correspond to species that, due to human activities, cross geographic and reproduction barriers and expand into new areas in large numbers. This spread into new ecosystems may have severe socio-economic or ecological impacts. The most efficient way to limit these impacts is to predict and avoid biological invasions before they occur by setting up appropriate management plans.The aim of this PhD thesis is to demonstrate that existing predictive models can be further developed and combined together to improve biological invasion predictions. All of the methods developed in this thesis have been applied to social Hymenoptera: ant species (Formicidae) and the Asian hornet (Vespa velutina nigrithorax), but they are generalizable to any other taxa. The questions asked are: can we predict future invader species? Can we improve the spatial predictions of their distribution? Can we predict invasive species impact?First, I show in this thesis that it is possible to develop a model that detects future invasive species, even before they have had the chance to be moved outside their native range. I apply this screening tool to more than 2000 ant species, provide a list of the 15 ant species that are highly likely to become invasive and map their global suitability to highlights the area the most at risk from these invasions. All continents are threatened by at least one of these potential invasions. Second, I set up a methodological framework to improve species distribution predictions by combining multi-scale drivers. I apply this method to the invasive Asian hornet, identify its high affinity habitats, and use this information to refine suitability maps. I show that integrating multiple drivers, while still respecting their scale of effect, produced a potential range 55.9% smaller than that predicted using a climatic model alone. Finally, I propose a method to predict invasive species impacts in a spatially explicit way and I apply it to the estimate the Asian hornet’s impact on honeybee colonies in France. To do so, I estimate the Asian hornet nest density across France and combine it with an agent-based hive model to estimate honeybee mortality risk. I show that up to 41% of the honeybee colonies are likely to collapse due to the Asian hornet.Overall, these studies demonstrate how modelling techniques can provide valuable inputs to improve invasive species management decision by offering tools to optimize prevention strategies and target areas, species or habitats where action is needed in priority. Biological invasions involve our scientific, political and cultural perceptions in an intricate way; this PhD thesis highlights the usefulness of bringing together modelling techniques and the rest of biological invasion knowledge to better grasp invasion science complexity.

En raison de leurs propriétés uniques, des nanoparticules industriellement fabriquées comme les nanotubes de carbone (NTC) ont révolutionné le domaine de la nanotechnologie. Il apparait nécessaire de développer des techniques d’investigation in vivo basées sur les propriétés intrinsèques de ces particules et permettant un suivi longitudinal pour évaluer leur risque après inhalation accidentelle par voie respiratoire. Un protocole d’IRM pulmonaire non-invasive utilisant l’hélium-3 hyper polarisé sous respiration spontanée a été développé en complément d’un protocole d’IRM systémique proton pour permettre la détection des NTC grâce à l’effet de susceptibilité magnétique induit par les impuretés de fer, associées aux nanotubes après leur exposition intra pulmonaire. Combiné avec l’IRM pulmonaire proton et des analyses en microscopie optique et électronique à différents temps d’investigation, ce protocole d’imagerie multimodale permet d’évaluer la biodistribution et l’impact biologique des NTC bruts après exposition intra pulmonaire.Une accentuation des réactions inflammatoires (granulomes multifocaux, dépôt de fibres de collagène…) avec le temps et la dose administrée a été observée.De l’évaluation de l’impact biologique des NTC après une exposition intra pulmonaire vers leurs applications biomédicales, les nanotubes de carbone avec leurs propriétés physicochimiques fascinantes et leur forme spécifique laissent entrevoir des applications potentielles en nanomédecine. La bio distribution et le profil pharmacologique des différents types de NTC ont été évalués longitudinalement par IRM et dosage dans le sang et les organes cibles après une injection intraveineuse, et leur impact biologique sur le métabolisme du foie a été examiné ex vivo par RMN haute résolution à l’angle magique (HR-MAS). Aucun signe de toxicité aiguë (variation du métabolisme du foie) n’a été observé et les analyses statistiques conduits sur les spectres RMN (tests PCA) ne montrent aucune différence entre les échantillons analysés et donc l’absence de discrimination entre les différents groupes par rapport aux animaux contrôles. / As novel engineered nanoparticles such as single-walled carbon nanotubes (SWCNT) are extensively used in nanotechnology due to their superior properties, it becomes critical to fully understand their biodistribution and effect when accidently inhaled. There fore, development of animaging technique which allow longitudinal in vivo follow-up of SWCNT effect based on their intrinsic properties is highly desirable. Non invasive free-breathing hyperpolarized 3He lung MRI protocol was developed complementary to proton systemic MR protocol to allow monitoring SWCNT based on their intrinsic iron impurities after intrapulmonary exposition. Combined toproton lung MRI and ex vivo optical and electron microscopy at different time points, this protocol represents a powerful multimodality imaging techniques which allows a full characterization of the biodistribution and biological impacts of iron containing SWCNT. SWCNT was found to produce granulomatous and inflammatory reactions in a time and dose dependent manner with their bio persistenc eafter intrapulmonary exposition.From biological impact evaluations after intrapulmonary exposition towards biomedical applications, SWCNT hold promise for applications in nanomedicine field with their distinct architecture and their novel physicochemical properties. The biodistribution and pharmacological profile of various well-dispersed pristine and functionalized SWCNT were assessed in blood and target tissues after their intra venous administration by longitudinal in vivo susceptibility weighted MRI and their potential effect on liver metabolism by ex vivo HRMAS 1H NMR. No presence ofacute toxicological effect (variation in liver metabolism) was observed confirmed by the absence of clustering in NMR spectra using Principal Component Analysis (specific biomarkers of toxicity).