De nos jours, la préservation de l’environnement est un enjeu majeur. Avant cette prise de conscience, de nombreux polluants ont été rejetés dans la nature. Parmi eux, les hydrocarbures sont très souvent rencontrés. Or, ils sont reconnus pour leur toxicité et leur persistance accrue. La mise en place de méthodes efficaces de dépollution est donc primordiale. Les méthodes classiques nécessitent l’excavation ou le pompage des zones contaminées, imposant un coût de dépollution élevé. C’est pourquoi des techniques de dépollution in-situ ont été développées afin de réduire ces coûts, tout en garantissant des rendements de dépollution efficaces. Les travaux menés durant cette Thèse ont permis de déterminer, pour plusieurs techniques de traitement, les facteurs limitants inhérents à la technique, mais aussi de quantifier le rôle du contact entre agents de traitement et zone polluée ou des effets densitaires. Les techniques in-situ utilisées sont : l’oxydation chimique in situ, le lavage par tensio-actifs, l’injection d’air (sparging) et le traitement thermique. Trois niveaux d’expérience ont été étudiés : le batch, la colonne et le pilote 3D. Les réacteurs fermés, ont permis la comparaison des oxydants en statiques face à une matrice plus ou moins riche en matières organiques. Les colonnes ont mis en avant l’influence du mode d'injection appliqué vis-à-vis des propriétés physico-chimiques des polluants (cinétique réactionnelle, pression de vapeur, température d’ébullition, etc.). Les pilotes 3D, d’un volume d’un 1 m3, ont permis de comparer les différentes techniques sur un milieu hétérogène présentant des zones peu perméables, difficiles à traiter. A partir des résultats acquis et de modélisation numérique des expériences, il est dorénavant possible de mieux ajuster la méthode de traitement et surtout de comparer différentes méthodes pour un contexte hydrogéologique donné. / Pollution of soils and aquifers by Diesel fuel compounds is a widespread remediation issue. Problems due to soil remediation are more and more difficult to treat. Hydrocarbons are often encountered. But they are known for their toxicity and increased persistence. The establishment of effective remediation methods is paramount. Conventional methods require excavation or pumping contaminated areas requiring a high abatement costs. That is why, in-situ remediation techniques have been developed to reduce these costs while ensuring efficient pollution control returns. The work done during this thesis has determined for several treatments, the limiting factors inherent the treatment, but also quantifies the role of contact between agents and pollutants or density effects. In-situ treatments are: in situ chemical oxidation, surfactants flushing, air sparging and thermic treatment. Three levels of experience were investigated: batch, column and 3D Pilot. Batchs, enabled the comparison of oxidants in sand and natural soil. The columns have highlighted the influence of the injection method applied occurs toward the physical and chemical properties of contaminants (reaction kinetics, vapor pressure, boiling temperature, etc.). 3D Pilot, have a volume of 1m3. They were used to compare the different treatments on a heterogeneous medium having low permeability zones, difficult to treat. From the results of numerical modeling and experiences, it is possible to adjust the treatment method and especially to compare different methods for a given hydrogeological context.

Natural killer (NK) cells, lymphocytes of the innate immune system, can recognize a wide array of cells via several receptors families such as Ly49 and NKR-P1. The Nkrp1 gene family encode for C-type lectin-like receptors which can recognize their ligands, Clr, on target cells. Nkrp1 and Clr genes are intertwined in the NK gene complex and are thus inherited together. The Nkrp1-Clr genes in 129S6 and BALB/c mouse strains show significant sequence polymorphism compared to those of C57BL/6 mice while the overall gene organization and gene number are conserved. RT-PCR was utilized to study the expression of individual Nkrp1-Clr genes. In situ hybridization was performed to validate expression results from RT-PCR, as well as to verify the cell types in which Nkrp1-Clr genes are expressed. Surprisingly, our expression studies reveal an interesting pattern of expression of Nkrp1 and Clr genes not only in lymphoid tissues but also in the epithelial cells of the intestine, kidney, eye and lung, the myocytes of the heart and skeletal muscle, and possibly some endothelial cells, indicating novel functions of NK cells in these tissues.

Le travail présenté dans ce manuscrit consiste en une contribution à l'étude de ces structures RTM par microscopie Raman, afin de mesurer certains paramètres tel que la réticulation, l'identification de composés chimiques, les contaminations, l'homogénéité d'additifs… mais aussi sur l'utilisation de ces mesures dans le cadre d'une modélisation numérique de ces structures. Cette Thèse de Doctorat s'inscrit dans un programme pour le remplacement des mesures actuelles intrusives, destructives et indirectes par une mesure in situ via un capteur Raman implanté dans l'outillage et à la construction du système en milieu industriel. Avec comme but d'optimisation par exemple les procédés de fabrication des pales d'éolienne, ponts de bateaux de garantir et valider des critères de qualité des pièces techniques à forte valeur ajoutée et enfin d'optimiser les caractéristiques physico-chimiques liées à la mis en œuvre dans l'outillage / The work presented in this manuscript is a contribution to the study of these structures RTM Raman microscopy, to measure parameters such as curing, the identification of chemical compounds, contamination, uniformity as addenda but ... also on the use of these measures in the framework of a numerical modelling of these structures. This Thesis is a program for replacing the current intrusive, destructive and indirect measurement in-situ Raman via a sensor implanted in the equipment and system construction in an industrial environment. With the aim of optimization processes such as manufacturing wind turbine blades, bridges boat guarantee and quality criteria of technical parts with high added value and to optimize the physical and chemical related to the mission implemented in tooling.

Amphibians are facing an extinction crisis, and in many cases it has become necessary to conserve species in captivity. Unfortunately, our understanding of the nutritional requirements of amphibians in captivity is currently limited. There have been anecdotal reports that captive bred amphibians have duller skin colouration than wild members of the same species. Many amphibians use carotenoid pigments in skin colouration. Carotenoids are yellow-red pigments synthesised by photosynthetic tissues, however vertebrates cannot synthesise them de novo and rely entirely on dietary sources. Reduced colour in captive bred amphibians could therefore result from limited carotenoid availability in the diet. Limited access to carotenoids could have further negative consequences on health and reproductive success since carotenoids are known to function in the immune, antioxidant and reproductive systems of other vertebrate taxa. The role of carotenoids in amphibian fitness is currently unknown, and the aim of this PhD was to assess the importance of carotenoids to anuran amphibians. Skin colour may be influenced by carotenoid availability, and it was therefore important to establish a suitable method for quantifying skin colour in amphibians. In Chapter 1 I assessed two methods for colour quantification, including digital photography and spectrometry. Neither method was significantly more accurate than the other, however I chose to use photography for my studies for reasons of practicality. In Chapters 2 and 3 I assessed the role of carotenoids in the reproductive systems of wild frogs. I found that carotenoid-based skin colouration was involved in the breeding behaviour of wild Agalychnis moreletii frogs. I found positive assortative mating by colour in that frogs were found mating with individuals with similar carotenoid-based colouration. This assortative mating by colour may be driven by mutual mate choice, or may have evolved to prevent mismatched pairing with a sympatric and phenotypically similar species (A. callidryas). I then analysed the carotenoid composition of eggs produced by wild A. moreletii and Phyllomedusa trinitatis, which are tree frogs with similar reproductive ecology but different egg deposition strategies: Agalychnis moreletii deposits green eggs on the surface of leaves while P. trinitatis wraps pale cream eggs in leaves. The concentration and diversity of carotenoids was significantly higher in A. moreletii than P. trinitatis and potential ecological explanations for this are discussed. In Chapter 4 I investigated carotenoid availability in the diet of captive amphibians by analysing the carotenoid composition of commonly used feeder-invertebrates. I assessed interspecific variation in carotenoid accumulation in three feeder-cricket species (Gryllus bimaculatus, Gryllodes sigillatus and Acheta domesticus), which were all fed one of three diets (wheat-bran, fish-food based diet, fresh fruit and vegetables). All three cricket species were a poor source of carotenoids unless they were gut-loaded on a carotenoid-rich diet. Nutrient retention over a two-day period was poor across species. Finally, there were significant interspecific differences in gut-loading capacity, with G. bimaculatus having the greatest capacity. This study shows that carotenoid availability to captive amphibians will be limited unless they are fed specific feeder invertebrate species, recently gut-loaded on carotenoid-rich foods. In Chapters 5, 6 and 7 I assessed the influence of carotenoids on fitness related traits in captive anurans. I firstly assessed colour degradation in captive-reared A. moreletii frogs and looked at whether skin colour could be improved through increased carotenoid availability in the diet. I found that carotenoid-based skin colour degraded quickly in captivity but could be improved through dietary supplementation with carotenoids, however there was a critical period during post-metamorphic growth for deposition of carotenoids in the skin. Next, I investigated the effect of carotenoids on larval growth and development, and post-metamorphic growth, development, skin colour and reproductive success in captive A. callidryas frogs. I found no direct effect of carotenoids during larval stages, however there were carry-over effects on post-metamorphic growth and skin colour. Increased post-metamorphic carotenoid availability positively influenced growth, skin colour and reproductive success. Similarly to A. moreletii, there was a critical period during post-metamorphic growth for deposition of carotenoids in the skin. Finally, I examined the protective potential of carotenoids in Silurana (Xenopus) tropicalis tadpoles that were exposed to ultraviolet (UV) light. Exposure to UV light significantly reduced tadpole survival and there was no evidence that carotenoids afforded any protection. Nevertheless, in tadpoles that were not exposed to enhanced UV light, carotenoids increased survival. Furthermore, carotenoids had a significantly positive effect on the developmental rate of tadpoles in both UV limited and UV enhanced environments. The studies in this PhD show that carotenoid availability has important consequences on fitness related traits in anuran amphibians, which include effects on growth, skin colour, reproductive success and survival. Carotenoid availability to captive amphibians will, however, be low unless they are provided with feeder invertebrates that have been recently gut-loaded on carotenoid-rich foods. These findings should be considered when recommendations are made on the nutritional requirements of amphibians in captivity as they could significantly improve the fitness of captive-bred individuals, and thus increase the success of ex situ conservation programmes.

MSCAGR (Animal Science) / Department of Animal Science / Soya bean (Glycine max) is a legume that is mostly cultivated for food grain which can be used as high-protein forage for grazing, haying or ensiling. The use of forage soya bean by small holder farmers is currently very limited. The objective of the current study was to evaluate the nutritive value of three trifoliate forage Soya bean cultivars (Locally denoted as 4-LF, PAN, and TGX). The study was carried out at the University of Venda where the soya beans were planted in 63 25L pots (21 pots for each cultivar) which were randomly placed on the floor of an open, wire-net protected house. Forage harvested at three growth stages (pre-anthesis, anthesis and postanthesis). Samples of the forage were analyzed for dry matter (DM), ash, crude protein (CP), neutral detergent fiber (NDF), acid detergent fiber (ADF) micro and macro minerals. Ruminal DM and CP degradability were evaluated in situ by incubation of samples within nylon bags (external dimension: 6 × 12 cm, pore size of 46 μm) in the rumen of three Bonsmara steers for 0, 6, 12, 16, 24, 48, 72, and 96 hours. Estimates of rapidly degradable fraction “a”, slowly degradable fraction “b”, constant outflow rate ‘c’ and the DM or CP degradability (p) at time (t) were estimated by fitting the degradability data into the exponential equation P = a + b (1 - e-ct) using the NEWAY computer programme. Parameters were subjected to ANOVA for a 3 X 3 factorial treatment arrangement using the General Linear Model procedures of MINITAB software (version 17 of 2014). Effective degradability ED) was estimated asED = a + bc at fractional outflow rates of k= (k +c) 2%, 5% and 8%. In vitro enzymatic DM and CP digestibility of rumen undegradable residues collected after 24 and 48-hour incubation was determined by simulating sequential gastro-small intestinal digestion. Cultivar PAN harvested post anthesis had significantly higher (p< 0.05) CP than other cultivars. The CP content increased with growth stage. Cultivar 4LF harvested preanthesis had significantly highest (p< 0.05) NDF. The cultivar had no significant effect (p> 0.05) on DM, ash, CP, NDF, ADF and minerals. Cultivar PAN harvested pre-anthesis had significantly highest (p< 0.05) Mg. The harvest stage significantly affected (p< 0.05) mineral content other than (p> 0.05) Zn and Cu. Cultivar TGX harvested pre-anthesis had significantly highest (p< 0.05) effective degradability of dry matter at k=0.08. Fraction ‘c’ and ED at k= 0.08 were lower (p> 0.05) in cultivar * growth stage interaction in dry matter degradability. Fraction ‘a’ for CP was highest (p< 0.05) for cultivar TGX harvested post-anthesis. Fraction ‘c’ was lower (p> 0.05) for cultivar 4LF harvested at anthesis stage. There was a significant effect (p< 0.05) on crude protein soluble fraction ‘c’ and effective degradability k=0.08 in cultivar and growth stage interaction. There was no significant interaction (p> 0.05) of the cultivar X growth stage on crude protein degradability at 48 hours, IVCPD at 24 and 48 hours with significant effect on crude protein degradation at 24 hours caused by cultivar TGX at pre-anthesis growth stage. In conclusion, growth stage increases the chemical composition of soya bean but does not affect digestibility. / NRF

Thermoplastics reinforced with continuous fibers are very promising building materials for the auto industry and consumer electronics to reduce the weight of vehicles and portable devices, and to deliver a high impact tolerance at the same time. Polypropylene is an abundant thermoplastic, and its glass fibers composites make a valuable solution that is suitable for mass production. But the adoption of such composites requires a deep understanding of their mechanical behavior under the relevant loading conditions. In this Ph.D. work, we aim to understand the damage process in continuous glass fiberreinforced polypropylene in detail. We will focus in particular on developing an approach for microscale observation of damage during the out-of-plane loading process and will use these observations for both qualitative and quantitative evaluation of the composite. We will apply our approach to two kinds of polypropylene composites, one of them is specially designed to withstand impact. The comparison between the two types of composites at slow and fast loading cases will shed some light on the effect of the polymer properties on the behavior of composites under out-of-plane loading.

Our reliance on semiconductors is on the rise with the ever growing use of electronics in our daily life. Organic-inorganic hybrid lead halide perovskites have emerged as a prime alternative to current standard and expensive semiconductors because of its use of abundant elements and the ease of solution processing. This thesis has shed light on the ink-to-solid conversion during the one-step solution process of hybrid perovskite formulations from DMF. We utilize a suite of in situ diagnostic probes including high speed optical microscopy, optical reflectance and absorbance, and grazing incidence wide angle x-ray scattering (GIWAXS), all performed during spin coating, to monitor the solution thinning behavior, changes in optical absorbance, and nucleation and growth of crystalline phases of the precursor and perovskite. The starting formulation experiences solvent-solute interactions within seconds of casting, leading to the formation of a wet gel with nanoscale features visible by in situ GIWAXS. The wet gel subsequently gives way to the formation of ordered precursor solvates (equimolar iodide and chloride solutions) or disordered precursor solvates (equimolar bromide or 3:1 chloride), depending upon the halide and MAI content. The ordered precursor solute phases are stable and retain the solvent for long durations, resulting in consistent conversion behavior to the perovskite phase and solar-cell performance. In this thesis, we develop a firm understanding of the solvent engineering process in which an anti-solvent is used during the coating process through the solvent mixture of GBL and DMSO in different ratios. It has been shown that solvent engineering produce pin hole-free films, justifying its wide adoption across the field. We then translate our learnings from the lab scale spin coating process to the industrial friendly blade coating process. Here we compare the ink solidification and film formation mechanisms of CH3NH3PbI3 in solutions we used to understand the key scientific insights through spin coating. We observe high-quality film formation for T > 100oC, namely in conditions which inhibit the formation of the crystalline intermediate complex phases. In doing so, we achieve fast and direct formation of the perovskite phase with solar cells yielding PCE > 17%.

If soil becomes so polluted that it can be assumed to pose unacceptable risks to health, theenvironment or natural resources, remedial action must be carried out. In 2006, aninventory study was compiled by the Swedish Environmental Protection Agency. The resultsshowed that more than 50% of the projects were completed via excavation of thecontaminated masses. Now 15 years later, the purpose of this report is to study remedialactions completed in Sweden over a 12-year period (2010–2021) and try to investigate howthe distribution of the methods used in practice reflects the development of knowledge onremediation. All 290 municipalities in Sweden were contacted and over 1000 reports ofremedial action were collected. Out of all 1000 reports only 114 was used due to the smallsize and short time allocated for this study. The result showed that in 113 of the 114 cases theremedial action was shown to be excavation, and, thus my conclusion is that excavation stillaccounted for the majority of remedial action methods used. It is not possible, based on theresults in this report, to determine exactly which factor or to what extent each factorcontributes to the majority of ex-situ remediation in Sweden. Probable reasons are the highcommercial availability of excavation remediation and traditions that exist in the industry,which means that it will not be possible for in-situ methods to establish themselves andbecome financially sustainable.

Permeable reactive biobarrier (PRBB) is a flow-through zone where microorganisms degrade contaminants in groundwater. Discontinuous presence of contaminants in groundwater causes performance loss of a PRBB in removing the target contaminant. A novel enricher reactor (ER) - PRBB system was developed to treat groundwater with contaminants that reappear after an absence period. ER is an offline reactor for enriching contaminant degraders, which were used for augmenting PRBB to maintain its performance after a period of contaminant absence. The ER-PRBB concept was initially applied to remove benzene that reappeared after absence periods of 10 and 25 days. PRBBs without ER augmentation experienced performance losses of up to 15% higher than ER-PRBBs. The role of inducer compounds in the ER to enrich bacteria that can degrade a mixture of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated with an objective to minimize the use of toxic chemicals as inducers. Three inducer types were studied: individual BTEX compounds, BTEX mixture, and benzoate (a non toxic and a common intermediate for BTEX biodegradation). Complete BTEX removal was observed for degraders enriched on all three inducer types; however, the removal rates were dependent on the inducer type. Degraders enriched on toluene and BTEX had the highest degradation rates for BTEX of 0.006 to 0.014 day-1 and 0.006 to 0.012 day-1, respectively, while degraders enriched on benzoate showed the lowest degradation rates of 0.004 to 0.009 day-1. The ER-PRBB technique was finally applied to address the performance loss of a PRBB due to inhibition interactions among BTEX, when the mixture reappeared after a 10 day absence period. The ER-PRBBs experienced minimal to no performance loss, while PRBBs without ER augmentation experienced performance losses between 11% and 35%. Presence of ethanol during the BTEX absence period increased the performance loss of PRBB for benzene removal. PRBBs augmented with degraders enriched on toluene alone overcame the inhibition interaction between benzene and toluene indicating that toluene can be used as a single effective inducer in an ER. The ER-PRBB was demonstrated to be a promising remediation technique and has potential for applications to a wide range of organic contaminants.

Cílem předložené diplomové práce byla in-situ příprava stříbrných nanočástic na kolagenové matrici jako antibakteriálního povlaku a studie vlivu podmínek přípravy na vlastnosti nanočástic, zejména jejich velikost, tvar, homogenita jejich distribuce a antibakteriální aktivita. V rámci práce byla rovněž sledována kinetika redukce stříbrných nanočástic z dusičnanu stříbrného a vliv teploty na její průběh. Připravený materiál a jeho vlastnosti byly analyzovány pomocí různých technik. UV-VIS absorpčních vlastností stříbra bylo využito pro kinetické studie redukce a uvolňování nanočástic. Pomocí rastrovací elektronové mikroskopie byla vyhodnocena homogenita stříbrného povlaku a přibližná velikost částic a jejich aglomerátů. Velikostní distribuce nanočástic byla pak přesně stanovena pomocí dynamického rozptylu světla. Pomocí infračervené spektrometrie s Fourierovou transformací s technikou úplného zeslabeného odrazu byla sledována interakce stříbra s funkčními, zejména karboxylovými skupinami. Termogravimetricky byla stanovena tepelná stabilita a procentuální obsah stříbra v materiálu. Vliv AgNPs povlaku na 3D strukturu kolagenního scaffoldu a fázový kontrast pro 3D zobrazovací techniky byl zkoumán pomocí rentgenové výpočetní nanotomografie. V neposlední řadě byla také stanovena antibakteriální aktivita připraveného materiálu a její závislost na koncentraci stříbra.