Chemical species carry information in two dimensions, in their concentrations and their isotopic signatures. The concentrations of metabolites or synthetic compounds describe the composition of a chemical or biological system, while isotopic signatures describe processes in the system by their reaction pathways, regulation, and responses to external stimuli. Stable isotopes are unique tracers of these processes because their natural abundances are modulated by isotope effects occurring in physical processes as well as in chemical reactions. Nuclear magnetic resonance (NMR) spectroscopy is a prime technique not only for identification and quantification of small molecules in complex systems but also for measuring intramolecular distribution of stable isotopes in metabolites and other small molecules. In this thesis, we use quantitative NMR in three fields: in food science, environmental pollutant tracing, and plant-climate science. The phospholipid (PL) composition of food samples is of high interest because of their nutritional value and technological properties. However, the analysis of PLs is difficult as they constitute only a small fraction of the total lipid contents in foods. Here, we developed a method to identify PLs and determine their composition in food samples, by combining a liquid-liquid extraction approach for enriching PLs, with specialized 31P,1H-COSY NMR experiments to identify and quantify PLs. Wide-spread pollution with synthetic compounds threatens the environment and human health. However, the fate of pollutants in the environment is often poorly understood. Using quantitative deuterium NMR spectroscopy, we showed for the nitrosamine NDMA and the pesticide DDT how intramolecular distributions (isotopomer patterns) of the heavy hydrogen isotope deuterium reveal mechanistic insight into transformation pathways of pollutants and organic compounds in general. Intramolecular isotope distributions can be used to trace a pollutant’s origin, to understand its environmental transformation pathways and to evaluate remediation approaches. The atmospheric CO2 concentration ([CO2]) is currently rising at an unprecedented rate and plant responses to this increase in [CO2] influence the global carbon cycle and will determine future plant productivity. To investigate long-term plant responses, we developed a method to elucidate metabolic fluxes from intramolecular deuterium distributions of metabolites that can be extracted from historic plant material. We show that the intramolecular deuterium distribution of plant glucose depends on growth [CO2] and reflects the magnitude of photorespiration, an important side reaction of photosynthesis. In historic plant samples, we observe that photorespiration decreased in annual crop plants and natural vegetation over the past century, with no observable acclimation, implying that photosynthesis increased. In tree-ring samples from all continents covering the past 60 – 700 years, we detected a significantly smaller decrease in photorespiration than expected. We conclude that the expected “CO2 fertilization” has occurred but was significantly less pronounced in trees, due to opposing effects. The presented applications show that intramolecular isotope distributions not only provide information about the origin and turnover of compounds but also about metabolic regulation. By extracting isotope distributions from archives of plant material, metabolic information can be obtained retrospectively, which allows studies over decades to millennia, timescales that are inaccessible with manipulation experiments.

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Many of the factors that shape contaminant accumulation profiles in marine mammals also strongly influence fat soluble vitamin accumulation. Vitamin A and E are essential fat soluble nutrients for numerous biological processes, including reproduction, growth, endocrine and immune function. Contaminants, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), can alter vitamin dynamics; as such these vitamins have been proposed as sensitive biomarkers of contaminant exposure in wildlife. In light of these considerations, the present thesis was aimed at better understanding the factors that influence the accumulation of lipophilic contaminants and vitamins in western Arctic beluga whales, and to determine if there was an interaction between the two. Maternal offloading to neonates during gestation reduced overall contaminant (PCBs and PBDEs) and vitamin (A and E) concentrations in reproductively active female whales. The PCB and PBDE congener pattern in mothers changed during gestation as a result of preferential transfer of light-low Log KOW congeners to the fetus. Overall, female beluga whales transferred approximately 11% of their PCB and PBDE blubber burden to their fetus. In terms of vitamins transfer, lower concentrations of tocopherols, retinol and retinyl esters were found in reproductively active females relative to males and reproductively inactive females. Metabolism was also found to be an important factor for contaminant and vitamin accumulation in beluga tissues. In a principal components analysis, PCBs clustered into metabolically-derived structure-activity groups, which separated along the first principal component according to its metabolic potential (metabolizable vs. recalcitrant). Contaminant-related up-regulation of metabolizing enzymes, including cytochrome P450, likely explained changes in the concentration and pattern of PCB and PBDE congeners, as well as hepatic, plasma, and blubber vitamin A and E. Since vitamins and lipophilic contaminants accumulated in beluga whales in the same way in relation to most biological processes, including sex, reproduction, size, condition, and feeding ecology, it was important to control and reduce the number of these confounding factors before claiming any tissue vitamin change was indeed the result of chemical exposure. In doing so, it was found that vitamin A and E homeostasis was influenced by PCBs in beluga whales, resulting in reduced hepatic storage and increased plasma and blubber concentrations. Overall, these results suggest that liver, plasma, and inner blubber vitamin A and E concentrations can be sensitive biomarkers of contaminant exposure only if major confounding effects are taken into consideration. The implications of altered vitamin dynamics on the health of beluga whales is unknown at this time; however, as Arctic marine mammals face continued stress related to climate change, increased human disturbance and emergence of infectious diseases, this study can serve as essential baseline data that can be used to monitor the health status of western Arctic beluga whales. / Graduate / 0383 / 0329 / 0768 / jpdesforges@gmail.com

Die Schadstoffsituation der Böden der Siedlungsgebiete von Annaberg-Buchholz und Aue (Erzgebirge) wurde mit unterschiedlichen methodischen Ansätzen und Interpolationsverfahren flächenhaft dargestellt und evaluiert. Festgestellt wurde, dass sich Punktinformationen zu Schadstoffgehalten auch in Siedlungsbereichen des Erzgebirges zumeist mit ausreichender Aussagesicherheit in Karten darstellen lassen. Dabei erwies sich keine der bislang bekannten Methoden für die Übertragung von Punktinformationen auf die Fläche als grundsätzlich vorteilhaft; jede Methode zeigte gebietsspezifisch und für einzelne Metalle Stärken und Schwächen. Erstmals kam ein Verfahren der künstlichen Intelligenz (Software advangeo®) erfolgreich zum Einsatz. Die Vorteile dieses Verfahrens zeigten sich gerade in sehr klein strukturierten Siedlungsbereichen und der Vielzahl von Einflussgrößen auf die Stoffgehalte. Damit ließ sich der Einfluss der oberflächennahen Erzgänge auf die Arsen-Konzentration der Böden im Siedlungsgebiet Annaberg gesichert abbilden. Die Erfahrungen aus den Testgebieten münden in Empfehlungen zur optimalen Anwendung der methodischen Ansätze und untersuchten Verfahren.

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Les particules de suies issues de moteur Diesel constituent un enjeu de santé publique et sont soumises à des réglementations de plus en plus strictes. Les constructeurs automobiles ont donc besoin de modèles capables de prédire l’évolution en nombre et en taille de ces particules de suies. Dans ce cadre, un modèle de suies basé sur une représentation sectionnelle de la phase solide est proposé dans cette thèse. Le choix de ce type d’approche est d’abord justifié par l’étude de l’état de l’art de la modélisation des suies. Le modèle de suies proposé est ensuite décrit. A chaque instant et en chaque point du maillage, les particules de suies sont réparties en sections selon leur taille et l’évolution de chaque section est gouvernée par : • une équation de transport;• des termes sources modélisant l’interaction avec la phase gazeuse (nucléation, condensation, croissance de surface et oxydation des suies);• des termes sources collisionnels permettant de représenter les interactions entre suies (condensation et coagulation). Ce modèle de suies nécessite donc la connaissance des concentrations locales et instantanées des précurseurs de suies et des espèces consommées par les schémas de réactions de surface des suies. Les schémas fournissant ces informations pour des conditions thermodynamiques rencontrées dans des moteurs Diesel comportant des centaines d’espèces et des milliers de réactions, ils ne peuvent être utilisés directement dans des calculs de CFD. Pour pallier cela, l’approche de tabulation de la chimie VPTHC (Variable Pressure Tabulated Homogeneous Chemistry) a été proposée. Cette approche est basée sur l’approche ADF (Approximated Diffusion Flame) qui a été simplifiée pour permettre son emploi couplé au modèle de suies sectionnel. Dans un premier temps, la capacité du modèle tabulé à reproduire la cinétique chimique a été validée par comparaison des résultats obtenus avec ceux de réacteurs homogènes avec loi de piston équivalents. Finalement, le modèle VPTHC, couplé au modèle de suies sectionnel, a été validé sur une base d’essais moteur dédiée avec des mesures de distribution en taille de suies à l’échappement. Cette base comporte des variations de durée d’injection, de pression d’injection et de taux d’EGR à la fois pour un carburant Diesel commercial et pour le carburant modèle utilisé dans les calculs. Les prédictions des débits horaires de suies et des distributions à l’échappement obtenues sont en bon accord avec les mesures.Ensuite, les résultats du modèle ont été comparés avec les mesures plus académiques et détaillées du Spray A de l’Engine Combustion Network, un spray à haute pression et température. Cette seconde validation expérimentale a permis l’étude du comportement du modèle dans des régimes transitoires. / Soot particles emitted by Diesel engines cause major public health issues. Car manufacturers need models able to predict soot number and size distribution to face the more and more stringent norms.In this context, a soot model based on a sectional description of the solid phase is proposed in this work. First, the type of approach is discussed on the base of state of the art of the current soot models. Then, the proposed model is described. At every location and time-step of the simulation, soot particles are split into sections depending on their size. Each section evolution is governed by: • a transport equation;• source terms representing its interaction with the gaseous phase (particle inception, condensation surface growth and oxidation);• source terms representing its interaction with other sections (condensation and coagulation).This soot model requires the knowledge of local and instantaneous concentrations of minor species involved in soot formation and evolution. The kinetic schemes including these species are composed of hundreds of species and thousands of reactions. It is not possible to use them in 3D-CFD simulations. Therefore, the tabulated approach VPTHC (Variable Pressure Tabulated Homogeneous Chemistry) has been proposed. This approach is based on the ADF approach (Approximated Diffusion Flame) which has been simplified in order to be coupled with the sectional soot model. First, this tabulated combustion model ability to reproduce detailed kinetic scheme prediction has been validated on variable pressure and mixture fraction homogeneous reactors designed for this purpose. Then, the models predictions have been compared to experimental measurement of soot yields and particle size distributions of Diesel engines. The validation database includes variations of injection duration, injection pressure and EGR rate performed with a commercial Diesel fuel as well as the surrogate used in simulations. The model predictions agree with the experiments for most cases. Finally, the model predictions have been compared on a more detailed and academical case with the Engine Combustion Network Spray A, a high pressure Diesel spray. This final experimental validation provides data to evaluate the model predictions in transient conditions.

Nowadays, in the field of energy production, particular attention must be paid to improving efficiency, reducing pollutants and fuel flexibility. To reach those goals, cogenerative systems represent an appealing solution. One of the most promising cogenerative systems available nowadays is the micro turbine, which provides reasonable electrical efficiency of about 30%, multi-fuel capability, low emission levels and heat recovery potential, and need minimum maintenance. Among the several options, micro gas turbines (mGT) are particularly interesting. Beside theuse of natural gas, other fuels like landfill gas, ethanol, industrial waste off-gases and other bio-based gases can be used. Moreover, it is possible to further improve the efficiencies and reduce the emissions for mGTs by paying particular attention at the design of the combustion chamber. To this goal, flameless combustion could be an interesting solution. Flameless combustion is able to provide high combustion efficiency with low NOx and soot emissions. The increasing interest in flameless combustion is motivated by its large fuel flexibility, representing a promising technology for low-calorific value fuels, high-calorific industrial wastes as well as in presence of hydrogen. Moreover, flameless combustion is very stableand noiseless, so it is suited for gas turbine applications where conventional operations may lead to significant thermo-acoustic instabilities (“humming”) and stresses. Flameless combustion needs the reactants to be preheated above their self-ignition temperature and enough inert combustion products to be entrained in the reaction region, in order to dilute the flame. As a result, the temperature field is more uniform than in traditional combustion systems, and it does not show high temperature peaks. Hence, NOx formation is suppressed as well as soot formation,due to the lean conditions, low temperatures and the large CO2 concentration in the exhausts.mGTs operating in flameless combustion regime represent a promising technology for the combined production of heat and power with increased efficiency, reduced pollutants emission and high fuel flexibility. The objective of the present Thesis is the design of a combustion chamber for amGT for residential applications. The design is performed employing CFD-tools. Thus, it is necessary to develop a reliable numerical model to use in the design process. Therefore, the first step of the Thesis consists in a series of validation studies, with the goal of selecting the most appropriate and reliable models to describe flameless combustion. The validation will be carried on three differenttest cases, which have different nominal powers and employ different gaseous fuels. The second part of the Thesis focuses on the design and optimization of the combustion chamber. Finally, the third part shows the experimental investigation of the aforementioned chamber.The study of those three cases shows that, to correctly predict the behavior of those systems, it is necessary to take into account both mixing and chemical kinetics. The best results have been obtained with the Eddy Dissipation Concept model, coupled with detailed kinetic schemes. As far as the NOx emissions are concerned, it is fundamental to include all the formation routes, i.e. thermal, prompt, via N2O and NNH route, to estimate properly the NOx production in flameless conditions.The aforementioned models have been used for the design and optimization of a combustion chamber for a mGT operating in flameless combustion regime. Both the design and the optimization have been carried out by means of CFD simulations and both are goal-oriented, meaning that they are carried out with the purpose of improving one or more performance indicators of the chamber, such as pollutants emissions, efficiency or pressure losses. The configuration that satisfies the criteria on the performance indicators has been built and investigated experimentally. The combustion chamber is stable and performs well in terms of emissions for a wide range of air inlet temperature and air-fuel equivalence ratio, lambda, values. Except for the condition closer to the stoichiometric one, both CO and NOx emissions are extremely low for all !and air inlet temperatures. Thechamber performs the best at its nominal operating condition, i.e. lambda = 3.5 and air inlet temperature 730 °C, In this case CO is 0 ppm and NOx is 5.6 ppm. The numerical model employed to describe the combustor performs quite well, except for the CO prediction, for all the conditions investigated. The final step of the present work is the application of a different kind of fuel, namely biogas. First the feasibility of such application has been evaluated using CFD calculations, and then the experimental evidence has been discussed. Due to a calibration error on the gas flow meter, it has not been possible to investigate the conditions of the design point (lambda = 3.5). Three other conditions have been examined,characterized by lower values of !closer to the stoichiometric conditions. Despite the relatively high values of NOx emissions due to the lower air excess and to the consequently higher temperatures, the combustion chamber has proven to be fuel flexible. Both ignition and stable combustion can be achieved also when biogas is burnt. Numerical simulations have also been performed; the results are in good agreement with the experimental evidence. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished