Biological invasion has become a major threat to economy, ecology, global biodiversity and ecosystem function of aquatic ecosystems. The main aim of the thesis was to study the effects of the zebra mussel (Dreissena polymorpha), a versatile invasive species, on phytoplankton dynamics and ecosystem function of lakes. In a first attempt, I compared the density of Dreissena and the physicochemical data of ecosystems that it invaded among North American and European lakes to identify important factors in its invasion success. Secondly, I investigated the impact of zebra mussels on phytoplankton community composition in a natural lake. Thirdly, I evaluated whether zebra mussel feeding behavior were affected by the presence of predatory waterborne cues. Finally, I examined the effect of Dreissena on seston stoichiometry. A Generalized Additive Model revealed that a joint effect of surface area, mean depth, total phosphorus and calcium concentrations can explain the variability in Dreissena density. Selective grazing by zebra mussels varied in relation to seasonal phytoplankton dynamics. Risk cues released by predators affected both feeding rate and prey selection of the mussels and had cascading indirect effects on phytoplankton biomass and community structure. I found that the flux in nutrients caused by differences in zebra mussel consumption lead to a variation in phytoplankton nutrient limitation. The flexibility of zebra mussel feeding behavior and variation in susceptibility among phytoplankton groups to mussel ingestion indicate that invading zebra mussels could alter phytoplankton community composition of lakes and have important ecosystem consequences. The results of this thesis contribute to the growing evidence that predators indirectly affect resource dynamics and food web structure through their non-lethal effects on consumers. The results suggested that zebra mussel can indirectly both reduce and increase the energy transfer efficiency from primary producers to upper trophic levels in the pelagic and benthic food webs, respectively.

Anthropogenic activities are increasing inorganic nitrogen (N) loadings to lakes in the northern hemisphere. In many boreal lakes phytoplankton are N limited, wherefore enhanced N input may affect the productivity of pelagic food webs. Simultaneously, global change causes increased inflows of terrestrial dissolved organic carbon (DOC) to boreal lakes. Between clear and humic lakes, whole lake primary and consumer production naturally differs. However, research is inconclusive as to what controls pelagic production in these lakes. Further, it is unclear how DOC affects the response of the pelagic food web to enhanced inorganic N availability. The overarching goal of this thesis was to study the effects of inorganic N and organic C for pelagic food webs in boreal lakes. In the thesis, I first identified the main drivers of pelagic production during summer in eight non-manipulated Swedish boreal lakes with naturally low or high DOC. Then I investigated how increased N availability affects the pelagic food chain, and how the response differs with DOC. Therefore, whole lake inorganic N fertilization experiments were conducted in six Swedish boreal lakes across a DOC gradient (low, medium, high) divided into three lake pairs (control, N enriched) with one reference and two impact years. In each lake, I also investigated the response of zooplankton growth using in situ mesocosm experiments excluding planktivores. I found that humic boreal lakes had lower phytoplankton production and biomass than clear water lakes. Further, phytoplankton community composition and food quality differed with DOC. However, high DOC did not reduce pelagic energy mobilization or zooplankton biomass, but promoted a higher dominance of cladoceran relative to copepod species. N addition clearly enhanced phytoplankton biomass and production in the experimental lakes. However, this stimulating N effect decreased with DOC as caused by light limitation. Further, the newly available phytoplankton energy derived from N addition was not efficiently transferred to zooplankton, which indicates a mismatch between producer energy supply and consumer energy use. Indeed, the mesocosm experiment revealed that decreased food quality of phytoplankton in response to N addition resulted in reduced food web performance, especially in clearer lakes. In humic lakes, zooplankton production and food web efficiency were clearly more resilient to N addition. In summary, my thesis suggests that any change in the landscape that enhances inorganic N availability will especially affect pelagic food webs in clear water lakes. In contrast, brownification will result in more lakes being resilient to eutrophication caused by enhanced N deposition.

Energy-Coupling-Factor (ECF)-Transporter sind Aufnahmesysteme für Vitamine und Übergangsmetallkationen in Prokaryoten. Sie bestehen aus den zwei unverwandten Membranproteinen S und T sowie einem Paar ABC-ATPasen (A). Die S-Einheit vermittelt die Substratspezifität. Die Kombination aus der T- und den A-Einheiten wird als ECF bezeichnet. In dieser Arbeit wurden Fragen zur kontrovers diskutierten Stöchiometrie der Untereinheiten von ECF-Transportern sowie zur zuvor postulierten Substrattransport-Funktion einzelner S-Komponenten auch ohne ECF untersucht. Dazu wurden der ECF-Biotintransporter BioMNY, mehrere natürlicherweise in Organismen ohne ECF existierende biotinspezifische S Einheiten (BioY) sowie zwei Vertreter der metallspezifischen ECF-Systeme genutzt. Die S-Einheit BioY des dreiteiligen Biotinimporters lag in vitro als Monomer und Dimer vor. Oligomeres BioY wurde außerdem in lebenden Bakterienzellen beobachtet. „Pull-down“-Experimente zeigten, dass die T Komponente BioN im BioMNY-Komplex zum Teil als Dimer vorlag. Wachstumsuntersuchungen bestätigten die Transportfunktion von acht solitär vorkommenden BioY. Die in vitro auch für diese BioY-Proteine nachgewiesene Dimerisierung könnte die Transportfunktion von BioY ohne ECF erklären. Die metallspezifischen S Einheiten CbiM/NikM interagieren mit für die Transportfunktion essentiellen, zusätzlichen Transmembranproteinen (N) und zeichnen sich durch eine Topologie mit sieben Transmembranhelices und einem extrem konservierten, weit in das Proteininnere hineinragenden N-Terminus aus. Die Metallbindestelle besteht aus vier Stickstoffatomen von Met1, His2 und His67 und wird durch ein Netz aus Wasserstoffbrückenbindungen stabilisiert. Die Transport¬funktion von CbiMN bzw. Nik(MN) ohne ECF wurde in vivo mittels des nickelabhängigen Enzyms Urease als Indikator für die intrazelluläre Nickelkonzentration verifiziert. Zum gegenwärtigen Zeitpunkt ist die Funktion der für den Transport essentiellen N-Komponente jedoch noch unklar. / Energy-coupling factor (ECF) transporters are uptake systems for vitamins and transition metal cations in prokaryotes. They consist of the two unrelated membrane proteins S and T, and a pair of ABC ATPases (A). The S unit mediates substrate specificity. The combination of the T and the A units is called ECF. In this thesis the controversially discussed stoichiometry of the subunits of ECF transporters and the postulated substrate transport function of solitary S units without ECF were analysed. For this purpose, the biotin-specific ECF transporter BioMNY, several biotin-specific S units (BioY) encoded in organisms lacking any recognizable ECF and two metal-specific ECF transporters were used. The S unit BioY of the tripartite biotin importer existed in vitro as monomer and dimer. Furthermore, oligomeric BioY was observed in living bacterial cells. Oligomerisation of a part of the T unit BioN in the BioMNY complex was shown by “pull-down”- experiments. Growth analyses confirmed the transport function of eight solitary BioY proteins. The dimerisation, also proved for these solitary BioY proteins in vitro, could be an explanation for the transport function of BioY without ECF. The metal-specific S units CbiM/NikM interact with additional and for the transport function essential transmembrane proteins (N). The S units consist of seven transmembrane helices and an extremely conserved N-terminus, which extends deeply into the protein. The metal-binding site consists of four nitrogen atoms from Met1, His2 and His67 and is stabilised by a series of hydrogen bonds. The transport function of CbiMN and Nik(MN) without ECF was verified respectively in vivo using the nickel-depending enzyme urease as an indicator for intracellular nickel concentration, respectively. However, the role of the N component, which is essential for transport activity, is currently under investigation.

<p>Циљ&nbsp; овог&nbsp; истраживања&nbsp; је био развој и валидација&nbsp; методе&nbsp; за&nbsp; процену&nbsp; комплексности стехиометријских проблема. Метода&nbsp; за&nbsp; процену&nbsp; комплексности&nbsp; укључује дизајн&nbsp; табеле&nbsp; за&nbsp; процену&nbsp; тежине&nbsp; и интерактивности&nbsp; концепата.&nbsp; Нумерички рејтинг когнитивне комплексности задатака на Тесту&nbsp; одређен&nbsp; је&nbsp; комбиновањем&nbsp; Табеле&nbsp; са методом Кнауса и сарадника. Метода за процену<br />комплексности&nbsp; стехиометријских&nbsp; проблемских задатака&nbsp; је&nbsp; валидирана&nbsp; статистички,корелационом&nbsp; анализом&nbsp; односа ученичког постигнућа и нумеричког рејтинга когнитивне комплексности&nbsp; проблема, као и односом уложеног&nbsp; менталног&nbsp; напора&nbsp; и&nbsp; процењене комплексности. При томе су добијене изузетно високе&nbsp; вредности&nbsp; корелационих коефицијената. Поред&nbsp; статистичке&nbsp; валидације&nbsp; Метода&nbsp; је подвргнута&nbsp; и&nbsp; валидацији&nbsp; применом&nbsp; Теорије простора знања. Применом предложене Методе конструисан&nbsp; је&nbsp; очекивани&nbsp; простор знања, а применом&nbsp; кориговане&nbsp; и&nbsp; минимизиране&nbsp; IITA конструисaн је реални простор знања из ученичких&nbsp; постигнућа&nbsp; на&nbsp; тесту.&nbsp;&nbsp;&nbsp; Простори знања су упоређен применом теорије графова. Очекивани&nbsp; и&nbsp; реални&nbsp; простор&nbsp; знања&nbsp; садрже велики&nbsp; број&nbsp; истих&nbsp; релација&nbsp; претпостављања, чиме&nbsp; је&nbsp; додатно&nbsp; потврђена&nbsp; валидност&nbsp; Методе.<br />Примена КСТ у валидацији Методе омогућила једа се увиде фине разлике између очекиваног и&nbsp; реалног&nbsp; простора&nbsp; знања&nbsp; на&nbsp; основу&nbsp; чега&nbsp; је указано&nbsp; на&nbsp; могућности&nbsp; даљег&nbsp; побољшања наставе стехиометрије.</p> / <p>Cilj&nbsp; ovog&nbsp; istraživanja&nbsp; je bio razvoj i validacija&nbsp; metode&nbsp; za&nbsp; procenu&nbsp; kompleksnosti stehiometrijskih problema. Metoda&nbsp; za&nbsp; procenu&nbsp; kompleksnosti&nbsp; uključuje dizajn&nbsp; tabele&nbsp; za&nbsp; procenu&nbsp; težine&nbsp; i interaktivnosti&nbsp; koncepata.&nbsp; Numerički rejting kognitivne kompleksnosti zadataka na Testu&nbsp; određen&nbsp; je&nbsp; kombinovanjem&nbsp; Tabele&nbsp; sa metodom Knausa i saradnika. Metoda za procenu<br />kompleksnosti&nbsp; stehiometrijskih&nbsp; problemskih zadataka&nbsp; je&nbsp; validirana&nbsp; statistički,korelacionom&nbsp; analizom&nbsp; odnosa učeničkog postignuća i numeričkog rejtinga kognitivne kompleksnosti&nbsp; problema, kao i odnosom uloženog&nbsp; mentalnog&nbsp; napora&nbsp; i&nbsp; procenjene kompleksnosti. Pri tome su dobijene izuzetno visoke&nbsp; vrednosti&nbsp; korelacionih koeficijenata. Pored&nbsp; statističke&nbsp; validacije&nbsp; Metoda&nbsp; je podvrgnuta&nbsp; i&nbsp; validaciji&nbsp; primenom&nbsp; Teorije prostora znanja. Primenom predložene Metode konstruisan&nbsp; je&nbsp; očekivani&nbsp; prostor znanja, a primenom&nbsp; korigovane&nbsp; i&nbsp; minimizirane&nbsp; IITA konstruisan je realni prostor znanja iz učeničkih&nbsp; postignuća&nbsp; na&nbsp; testu.&nbsp;&nbsp;&nbsp; Prostori znanja su upoređen primenom teorije grafova. Očekivani&nbsp; i&nbsp; realni&nbsp; prostor&nbsp; znanja&nbsp; sadrže veliki&nbsp; broj&nbsp; istih&nbsp; relacija&nbsp; pretpostavljanja, čime&nbsp; je&nbsp; dodatno&nbsp; potvrđena&nbsp; validnost&nbsp; Metode.<br />Primena KST u validaciji Metode omogućila jeda se uvide fine razlike između očekivanog i&nbsp; realnog&nbsp; prostora&nbsp; znanja&nbsp; na&nbsp; osnovu&nbsp; čega&nbsp; je ukazano&nbsp; na&nbsp; mogućnosti&nbsp; daljeg&nbsp; poboljšanja nastave stehiometrije.</p> / <p>The&nbsp; main goal&nbsp; of&nbsp; this&nbsp; dissertation&nbsp; was&nbsp; to develop and validate the Method for estimation of the complexity of stoichiometric problems. The&nbsp; Method&nbsp; for&nbsp;&nbsp; assessment&nbsp; of&nbsp; complexity involves the design of a table for assessment of difficulty and interactivity of the concepts. The numerical rating of the cognitive complexity of tasks on the Test is determined by combining the Table with the Knaus et al. (2011) method. Method&nbsp; for&nbsp; estimation&nbsp; of&nbsp; the&nbsp; complexity&nbsp; of stoichiometric&nbsp; problems&nbsp; is validated&nbsp; by&nbsp; a statistically&nbsp; significant correlation analysis between students&#39; performances and cognitive complexity,&nbsp; as&nbsp; well&nbsp; as&nbsp; between&nbsp; students&#39;evaluation &nbsp; of&nbsp; invested&nbsp; mental&nbsp; effort&nbsp; and cognitive&nbsp; complexity. In doing so, extremely high values&nbsp; of&nbsp; correlation&nbsp; coefficients&nbsp; were obtained.&nbsp; In addition to statistical validation,&nbsp; the Method was&nbsp; subjected&nbsp; to&nbsp; validation&nbsp; using&nbsp; the Knowledge Space Theory. Using the proposed Method,&nbsp; the&nbsp; expected&nbsp; knowledge&nbsp; space&nbsp; was constructed, and by applying the corrected and minimized&nbsp; IITA,&nbsp; a&nbsp; real&nbsp; knowledge&nbsp; space from student&nbsp; achievement&nbsp; on&nbsp; the&nbsp; test&nbsp; was constructed. Knowledge&nbsp; spaces&nbsp; are&nbsp; compared using&nbsp; graph difference.&nbsp; The&nbsp; expected&nbsp; and&nbsp; real&nbsp; knowledge space&nbsp; contained&nbsp; a&nbsp; large&nbsp; number&nbsp; of&nbsp; the&nbsp; same surmise relations, which additionally confirms the validity of Method. Differences between theknowledge&nbsp; space&nbsp; pointed&nbsp; to&nbsp; some&nbsp; facts&nbsp; that teachers often do not see with their students.The&nbsp; application&nbsp; of&nbsp; KST&nbsp; in&nbsp; the&nbsp; Method validation pointed out the fine differencesbetween&nbsp; the&nbsp; expected&nbsp; and&nbsp; real&nbsp; knowledge space,&nbsp; indicating&nbsp; possibilities&nbsp; for&nbsp; further improvement of stoichiometry teaching.</p>

La Méditerranée est caractérisée par une grande variété de régimes trophiques qui s'explique par les apports fluviaux, les ratios azote/phosphore particulièrement élevés dans le bassin oriental, et par les processus hydrodynamiques en particulier le mélange vertical dans les régions situées au nord. Cette thèse qui s'inscrit dans le cadre du projet MerMEX, composante du chantier MISTRALS, a pour objectif l'étude des cycles biogéochimiques en Méditerranée. Elle s'appuie en particulier sur les observations acquises dans le cadre du projet DeWEx et sur la modélisation couplée physique biogéochimie 3D. À l'échelle du bassin et à l'échelle régionale du sous-bassin occidental. La première étude à l'échelle du bassin sur une période de 10 ans a permis d'effectuer une classification de régimes biogéochimiques, en fonction de leurs caractéristiques physiques et biogéochimiques. Les zones oligotrophes présentes au sud du bassin oriental et occidental sont caractérisées par une faible efflorescence et par de grandes profondeurs de nutriclines. Tandis qu'au nord du bassin, au large de Rhodes, en mer Adriatique et dans le bassin Liguro-provençal, le régime oligotrophe estival est suivi en hiver par une dynamique verticale intense, la convection profonde. Cette dernière est considérée comme le moteur de la circulation thermohaline. Elle entraine un enrichissement des eaux de surface en sels nutritifs qui permet une efflorescence rapide et intense au printemps. L'océan Atlantique représente une source de matière organique pour la Méditerranée. Cette mer représente en revanche une source de sels nutritifs pour l'Atlantique. Ensuite, un modèle à très haute résolution a été imbriqué dans le modèle de bassin pour quantifier les processus physiques et biologiques qui déterminent la variabilité temporelle de la disponibilité et de la stœchiométrie des sels nutritifs en Méditerranée nord-occidentale. La convection profonde hivernale entraîne une homogénéisation des propriétés biogéochimiques sur la colonne d'eau, et une stœchiométrie vers des valeurs estivales. Cette région bascule d'un régime d'eutrophie lors de la convection profonde vers un régime oligotrophe après le bloom de printemps. Lors du premier régime la production primaire est dominée par une production nouvelle en surface, alors que lors du deuxième régime la production phytoplanctonique de subsurface est essentiellement régénérée. Les masses d'eau adjacentes à la zone de convection et celles situées au sud sont caractérisées par une dominance de production régénérée toute l'année. Une partie de la matière organique particulaire est exportée en dessous de la couche épipélagique. Cet export de matière organique est variable et est fortement lié à la dynamique verticale des masses d'eau. / The Mediterranean Sea is characterized by various trophic regimes due to river inputs, as well as heterogeneous nitrogen to phosphorus ratios and hydrodynamic processes, in particular vertical mixing. The objective of this thesis that was performed in the framework of the MISTRALS program is the study of the biogeochemical cycles of these various regimes that composed the Mediterranean. It is mainly based on the in situ observations collected during DeWEx project and on 3D physical/biogeochemical modeling at the scale of the entire basin and at the regional of the western sub-basin. The first study is a ten-year basin scale study which allows an ecological classification, giving bioregions in function of their physical and biogeochemical properties. Southern oligotrophic areas in both eastern and western sub-basins are characterized by low efflorescence and deep nutriclines. While in the north, near Rhodes Island, in the southern Adriatic Sea and in the Liguro-Provencal sub-basin, the summer oligotrophic regime is altered annually by intense vertical dynamics, the deep convection. This process is considered as a driving force of the thermohaline circulation and entrains an enrichment of nutrients in surface layer which allows rapid and intense blooms in spring. The Mediterranean receives organic matter from the Atlantic Ocean, while, it is a source of inorganic matter for the Atlantic. In a second part of this thesis, a high resolution model on the western sub-basin was embedded in the basin model to quantify the physical and biological processes that determine the temporal variability of the nutrient stocks and their stoichiometry. The north-western Mediterranean turns from an eutrophic regime during deep convection to an oligotrophic regime after the spring bloom. During the eutrophic regime new production dominates the primary production at the surface while during the oligotrophic regime primary production is essentially associated to subsurface regenerated one. Adjacent water masses of the convection zone and west-southern regions are characterized by a dominance of regenerated production all over the year.

Malgré l'importance reconnue des forêts tropicales humides dans la régulation du climat et du cycle global du carbone, la biogéochimie des forêts tropicales reste moins bien appréhendée que celle d'autres biomes. En particulier, il existe encore de larges incertitudes quant aux limitations nutritives des processus ou encore sur le rôle de la diversité pour les fonctions écosystémiques. La diversité spécifique élevée des arbres de forêt amazonienne se traduit localement par une forte hétérogénéité de la qualité des apports de litière foliaire, ces apports constituant une ressource primordiale d'énergie et de nutriments pour les organismes saprophages. Cependant les conséquences d'une telle hétérogénéité des litières pour le fonctionnement souterrain sont encore peu connues dans ce milieu. L'objectif de cette thèse est d'établir une compréhension mécaniste des effets de la qualité des apports de litière ainsi que du rôle de leur diversité sur la décomposition. J'ai combiné des fertilisations factorielles de carbone (C), d'azote (N) et de phosphore (P) à l'utilisation d'une large gamme de stœchiométrie C : N : P des litières (issues de différentes espèces d'arbres) en forêt tropicale de Guyane française et en laboratoire pour évaluer la nature et l'étendue des contraintes énergétiques et nutritives imposées par la qualité des litières sur les activités des décomposeurs. Bien que la perte en masse des litières dans ce système d'étude apparait largement expliquée par la qualité des différentes formes de C des litières, suggérant un fort contrôle de la disponibilité en énergie sur la décomposition, les ajouts externes de C n'ont pas permis de mettre en évidence cette apparente contrainte énergétique. Cependant, je montre que la décomposition des litières tropicales est limitée conjointement par N et P, et que l'amplitude de cette co-limitation est fortement reliée à la disponibilité en P des litières ainsi qu'à leur stœchiométrie N : P. Ainsi, même si le P apparaît plus profondément limitant dans ce système (en accord avec l'hypothèse généralement admise d'un fort déficit en P en forêt tropicale humide), l'accès à l'N foliaire semble également contraindre la décomposition. Je mets également en évidence des effets de diversité des mélanges de litières, pour la plupart synergiques (les taux de décomposition observés des mélanges étaient généralement plus élevés que ceux prédits à partir des taux de décomposition des espèces seules) et largement amplifiés par la présence de la faune détritivore. De plus, en présence de faune, il apparait qu'une forte dissimilarité stœchiométrique dans les mélanges de litières favorise des effets synergiques. Autrement dit, l'association de litières ayant des stœchiométries dissimilaires semble favoriser un meilleur équilibre nutritionnel pour la faune saprophage, stimulant ainsi la décomposition. Finalement, je montre que ces effets synergiques dans les mélanges sont renforcés à travers les effets à long terme des apports de litières issus des différentes espèces d'arbres contribuant à ces mélanges. Ce résultat suggère que la complémentarité de l'utilisation des ressources émerge à travers des interactions à long terme entre les arbres et les organismes décomposeurs. / The high tree species diversity in Amazonian rainforest translates into a high variation of leaf litter quality input to the soil. These inputs constitute a major resource of nutrients and energy for saprophageous organisms, particularly in tropical rainforests growing on old and highly weathered soils and consequently impoverished in rock-derived mineral nutrients. However the consequences of such leaf litter heterogeneity for belowground functioning are still poorly understood. In this thesis, I aim to develop a better mechanistic understanding of leaf litter quality effects and litter diversity on decomposition. Using a factorial fertilization of carbon (C), nitrogen (N), phosphorus (P) and a wide range of leaf litter C : N : P stoichiometries (derived from different tree species) in French Guiana rainforest and in laboratory, I aim to assess the nature and the extent of energetic and nutritional constraints imposed by litter quality on decomposer activities. Although the litter mass loss in this study system is greatly explained by the litter C quality, suggesting a strong control of energy availability on decomposition, external C additions do not alleviate this apparent energetic constraint. However, I find that litter decomposition is conjointly limited by N and P and that the extent of this NP co-limitation is widely related to leaf litter P content and to litter N : P stoichiometry. Thus, even if P appears more profoundly limiting in this system (in accordance to the well-recognized P deficiency hypothesis in tropical rainforest), the litter N access seems also constrain the decomposition. Moreover, I find significant litter diversity effects in litter mixtures and most of them are synergistics (observed mass loss in mixture was more often higher than predicted mass loss on the basis of single species decomposition). These litter diversity effects are largely higher in presence of soil fauna and increase with stoichiometric dissimilarity in mixtures. In other words, the association of stoichiometrically dissimilar litter appear promote a better nutritional balance for the saprophageaous fauna, and thus, stimulate the decomposition. Finally, I show that synergistic effects in mixtures are reinforced toward long-term presence of tree species contributing to the litter mixtures. This result suggest that complementarity effects on mixed litter decomposition may emerge through long-term interactions between aboveground and belowground biota.

Les cours d’eau de tête de bassin versant, malgré leurs tailles réduites, jouent des rôles importants pour le fonctionnement des milieux situés en aval, et rendent de nombreux services écologiques. Depuis l’émergence du River Continuum Concept, le fonctionnement de ces cours d’eau est considéré comme reposant principalement sur les apports allochtones de matière organique détritique par opposition aux écosystèmes aval de plus grande taille dans lesquels la production primaire autochtone est considérée comme prépondérante. Bien que les détritus soient, par définition, des ressources de moindre qualité pour leurs consommateurs que les végétaux vivants, le rôle des facteurs qui limitent la production biologique et les processus fonctionnels dans ces écosystèmes détritiques reste encore peu exploré. Par exemple la carence en éléments minéraux essentiels (notamment en azote et en phosphore) dans les détritus peut limiter le développement des organismes vivants dans les cours d’eau. De ce fait, la disponibilité en éléments minéraux dans la colonne d’eau, en stimulant la croissance, l’activité des décomposeurs et la qualité élémentaire des ressources par le processus d’immobilisation microbienne, pourrait contrôler pour partie les processus écologiques en jeu dans ces écosystèmes. En étudiant in situ la réponse des communautés microbiennes aux nutriments le long d’un gradient d’occupation des sols, nos travaux ont mis en évidence un effet positif des éléments dissous (N et P) sur la décomposition des litières et les activités enzymatiques des décomposeurs, et ce même pour les niveaux en nutriments les plus élevés du gradient, pour lesquels des effets inverses étaient attendus. Indépendamment, dans des cours d’eau anciennement soumis à de forts dépôts acidifiants, nous avons pu observer une récupération du processus de décomposition des litières. Néanmoins, cette restauration s’accompagnant d’un appauvrissement marqué en N, des perturbations du fonctionnement de ces cours d’eau pourrait se manifester à terme. Le rôle de la production primaire dans les cours d’eau de tête de bassin versant a ensuite été questionné. En effet, bien qu’étant mineur quantitativement, l’apport de carbone de forte qualité pourrait jouer un rôle non négligeable sur le fonctionnement des cours d’eau de tête de bassin versant. En particulier, l’importance et le rôle des apports en acides gras polyinsaturés (AGPI) via les biofilms phototrophes ont été questionnés. En se basant sur un suivi de terrain sur 15 cours d’eau des Vosges le long d’un gradient d’acidification, nos recherches ont tout d’abord pu mettre en évidence la présence de biofilms diatomiques riches en AGPI, malgré le caractère très forestier de ces cours d’eau. Dans un second temps, une expérience en conditions contrôlées a permis d’observer le rôle positif des apports, mêmes faibles, de ressources diatomiques sur la croissance et la survie du crustacé amphipode Gammarus fossarum. Sans cet apport, ces organismes se sont avérés incapables de maintenir leurs niveaux internes d’AGPI, suggérant qu’une consommation de producteurs primaires autochtones était indispensable à ces organismes détritivores. Nos résultats ont ainsi pu mettre en évidence les rôles fondamentaux que peuvent jouer la disponibilité en éléments dissous (N et P) et la qualité du carbone dans les ressources sur la production biologique et sur le processus de décomposition des litières dans les cours d’eau de tête de bassin versant. Ces résultats appellent désormais à investiguer plus profondément les interactions entre ces deux facteurs limitants, et à comprendre dans quels contextes l’un des facteurs pourrait suppléer l’autre. En particulier, il sera intéressant de rechercher comment diverses perturbations anthropiques (xénobiotiques, réchauffement climatique etc…) pourraient affecter l’intensité ou la nature de ces limitations / Despite their reduced sizes, headwater streams play important roles in the functioning of downstream ecosystems and provide numerous ecological services. Since the River Continuum Concept, the functioning of these streams has been considered as mainly relying on allochthonous supplies of detrital organic matter for their functioning, in contrast with downstream ecosystems of larger size where primary production is considered to be predominant. Despite that detritus represent, by definition, a resource of lower quality for its consumers than living plants, the nature of the factors limiting the biological production and functional processes in these detrital ecosystems remains sparsely explored. First, the lack of essential elements (in particular nitrogen and phosphorus) in detritus could be a major constraint for the development of living organisms in streams. As a result, the availability of mineral elements in the water column, by stimulating the growth and activity of decomposers, but also by increasing the elemental quality of resources through microbial immobilization, could control ecological processes in a higher extent than previously believed in these ecosystems. By studying in situ, the response of microorganisms to nutrients availability along a land-use gradient, our results have shown a positive effect of the dissolved elements (N and P) on the decomposition of leaf litters and the enzymatic activities of the decomposers, even for the highest nutrient levels of the gradient, for which adverse effects were expected. Independently, in streams formerly subjected to acidification, we observed a recovery of the process of leaf litter decomposition. Nevertheless, this recovery was accompanied by a marked N reduction in the ecosystem, huge changes in stream functioning might be expected in the medium to long term. The role of autochthonous primary production was then questioned. Indeed, while being quantitatively minor, this contribution of high quality carbon may play a significant role in the functioning of headwater streams. In particular, the importance and role of polyunsaturated fatty acid (PUFA) intakes via phototrophic biofilms was questioned. Based on a field survey of 15 rivers in the Vosges Mountains along an acidification gradient, our results first showed the presence of diatomic biofilms rich in PUFA, despite these streams are clearly in a forested context. In a second step, an experimentation carried out under controlled conditions permitted to observe the positive role of diatomic resources, even in low concentrations, on the growth and survival of the crustacean amphipod Gammarus fossarum. Without this input, these organisms were unable to maintain their internal levels of PUFAs, suggesting that the consumption of autochthonous primary producers might be essential for these detritivore organisms. All our results permit to highlight the fundamental roles that can be played by the availability of dissolved elements (N and P) and the carbon quality of the resources on the biological production and on leaf litter decomposition in headwater streams. These results stress the need for more profound investigation of the interactions between these two limiting factors, and for understanding in which contexts one factor could supplement the other. In particular, it will be interesting to investigate to what extent various anthropogenic disturbances (xenobiotics, global warming, etc...) could affect the intensity or the nature of these limitations

<p>Biological invasion has become a major threat to economy, ecology, global biodiversity and ecosystem function of aquatic ecosystems. The main aim of the thesis was to study the effects of the zebra mussel <i>(Dreissena polymorpha)</i>, a versatile invasive species, on phytoplankton dynamics and ecosystem function of lakes. </p><p>In a first attempt, I compared the density of <i>Dreissena</i> and the physicochemical data of ecosystems that it invaded among North American and European lakes to identify important factors in its invasion success. Secondly, I investigated the impact of zebra mussels on phytoplankton community composition in a natural lake. Thirdly, I evaluated whether zebra mussel feeding behavior were affected by the presence of predatory waterborne cues. Finally, I examined the effect of <i>Dreissena</i> on seston stoichiometry.</p><p>A Generalized Additive Model revealed that a joint effect of surface area, mean depth, total phosphorus and calcium concentrations can explain the variability in <i>Dreissena</i> density. Selective grazing by zebra mussels varied in relation to seasonal phytoplankton dynamics. Risk cues released by predators affected both feeding rate and prey selection of the mussels and had cascading indirect effects on phytoplankton biomass and community structure. I found that the flux in nutrients caused by differences in zebra mussel consumption lead to a variation in phytoplankton nutrient limitation.</p><p>The flexibility of zebra mussel feeding behavior and variation in susceptibility among phytoplankton groups to mussel ingestion indicate that invading zebra mussels could alter phytoplankton community composition of lakes and have important ecosystem consequences. The results of this thesis contribute to the growing evidence that predators indirectly affect resource dynamics and food web structure through their non-lethal effects on consumers. The results suggested that zebra mussel can indirectly both reduce and increase the energy transfer efficiency from primary producers to upper trophic levels in the pelagic and benthic food webs, respectively. </p>

The surface charges of cellulosic fibers contribute to several papermaking operations that influence the manufacture and final properties of paper. This thesis investigates the effect of the surface charges on wet-end chemistry, e.g. through the interaction of cationic polyelectrolytes with the fiber surface charges, and on the network strength of pulp suspensions. The polyelectrolyte titration method was used to investigate the interaction of the fiber charges with cationic polyelectrolytes. Techniques were developed to fluorescent label the adsorbing cationic polyelectrolyte in order to visualize the adsorption behavior. Fluorescent confocal laser scanning microscopy (CLSM) was used to determine the extent to which the cationic polyelectrolyte adsorbs into the porous fiber wall. It was shown that the polyelectrolyte charge density limits the adsorption to the surface under electrolyte-free conditions. Adsorption into the fiber wall only occurs for two conditions: 1) if the molecular mass is sufficiently low or 2) the electrolyte concentration is high enough to screen the charges along the polyelectrolyte backbone but not the interactions between the polyelectrolyte and the fiber charges. Aside from the polyelectrolyte properties, the fiber charge density contributes to the adsorption behavior of cationic polyelectrolytes. The fiber charge profile was altered by bulk and surface carboxymethylation. The electrolyte concentration at which a deviation from 1:1 stoichiometry occurs was shown to be dependent on the amount of surface charges, such that the deviation in stoichiometry occurs at a higher electrolyte concentration for pulps having a higher surface charge. A hypothesis was developed to test the conditions at which the deviation in adsorption stoichiometry occurs, which was defined as the critical electrolyte concentration (CEC). It was found that the CEC corresponded to the electrolyte concentration at which the distance between the fiber charges was on the order of the Debye length. Electron spectroscopy for chemical analysis (ESCA) was used as an independent calibration procedure to validate for which a 1:1 stoichiometry occurs. The analysis with ESCA agreed well with the polyelectrolyte titration method for measurement of fiber surface charges. When measured under appropriate conditions, i.e. electrolyte concentration and molecular properties, the fiber surface charge can accurately be measured by the polyelectrolyte titration method. The charge profiles of various pulp types and treatments were also examined. Having been established as a valid technique, the polyelectrolyte titration method was again used to measure the surface charge while conductometric titration was used to measure the total charge content. The amount of bulk and surface charges vary depending on the pulping method and type of wood, although the ratio between the bulk and surface charge (i.e. the charge ratio) is similar for chemical pulps. The mechanical pulp has a higher charge ratio because it contains more fines material than chemical pulp. Bleaching of the chemical pulp decreases the amount of bulk and surface charges, although the charge ratio remains essentially constant. However, methods such as beating or carboxymethyl cellulose (CMC) grafting are available to increase the charge ratio. The effect of the charge profile on fiber-fiber interactions was studied on both a microscopic and macroscopic level. Colloidal probe microscopy (CPM) was used to investigate the microscopic interactions between two cellulose surfaces. Cellulose surfaces, prepared by spin-coating a dissolving pulp onto silica, were used to model the fiber surface, which is too rough for surface force measurements. The charge density of the model surface was increased by CMC grafting. Results showed that increasing the surface charge density created large electrosteric repulsions, due to CMC the chains protruding out from the surface. These interactions on the microscopic scale affect the fiber network strength, which was measured with a parallel plate rheometer. When the repulsion is increased between the fibers, caused by the increase in the surface charge, fiber flocs break apart more easily due to a reduced friction between the fiber surfaces. The forces acting on the fiber network can also be mechanical in origin. The fiber length and flexibility were altered in order to study the influence of mechanical surface linking and elastic fiber bending on the fiber network strength. Using the storage modulus (G’0) as a measure of fiber network strength, longer fibers were found to create a stronger network due to an increased amount of fiber contacts. Flexible fibers have a lower network strength than stiff fibers because the fibers come to rest in a less strained position such that the the influence of elastic fiber bending on the fiber network strength is predominant. / QC 20100831

The major objectives of this study were to investigate the antioxidant properties of flaxseed lignans secoisolariciresinol (SECO 2) and secoisolariciresinol diglycoside (SDG 1) and their major oxidative compounds using 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH 47) in an in vitro model of lipid peroxidation. This investigation was facilitated by the structural elucidation of the major oxidative compounds and the ability of flaxseed lignans to delay the onset of oxidation in two model systems. <p>This study showed that SECO 2 oxidation occurs at the aromatic (4-OH) and aliphatic (9-OH) hydroxyl groups. Conversely for SDG 1, only compounds derived from the oxidation of aromatic hydroxyl groups were obtained because the 9-OH position is glucosylated. <p>SECO 2 oxidation with AAPH 47 showed that the intermediate 2a is most likely involved in the generation of early-forming (48 and 52) and 2c for the formation of late-forming (49, 50 and 51) oxidation compounds. Compound 48 is formed from dimerization of 2a that is converted to 52 and then to 51. Compound 50 was formed by the addition of a carbon-centre free radical of AAPH (AP radical) to 2c. Compounds 50 and 51 trap carbon-centered AP radicals supporting SECO 2 as a chain-breaking antioxidant and AAPH 47 as a proper model for study of SECO 2 oxidation in vitro. <p>SDG 1 oxidation with AAPH 47 indicated that intermediates 1b and 1c are most likely involved for the formation of early forming compounds (55 and 58) and 1a leads to the late forming compounds (56 and 57). Compound 55 is a result of dimerization. Compound 56 may be directly formed via intermediate radical 1a by adding AP free radicals. Compound 56 was a stable non-radical compound that could trap AP free radicals, thereby supporting SDG 1 as a chain-breaking antioxidant. Hydrogen abstraction from 4-hydroxyl yielded the radical 1a and hydroxyl radical addition to 1a yielded 57. Compound 58 formed from the addition of OH or H2O to 1c. <p>This study demonstrated that AAPH 47 produces carbon-centred AP radicals upon thermal decomposition and mimics the formation of lipid peroxyl radicals. Interaction of carbon-centred AP radicals with SECO 2 and SDG 1 provides a good model to study the antioxidant reactions of SECO 2 in vitro. p*The relative antioxidant capacity of the flaxseed lignans versus BHT 17, in two model systems, was determined. The stoichiometric ratio for SECO 2 and SDG 1 were 1.5 and 1.1-1.2, respectively, compared to BHT 17 (2.0). The induction time by Rancimat analyzer measured inhibition of autoxidation mediated by flaxseed lignans SECO, SDG and SDG polymer in comparison with BHT 17. The induction time data demonstrated that SECO 2 protected canola oil better than either SDG 1 or SDG polymer 3. <p>These results are important for better understanding about the chemistry behind flaxseed lignan antioxidant activities. This study provided useful evidence that flaxseed lignans can be used as natural antioxidants.