Une étude conjointe du CEA et d'AREVA la Hague a montré qu'une des voies d'amélioration majeure des usines de traitement/recyclage du combustible nucléaire usagé, actuelles et futures, concerné le domaine de l'analyse. En effet, le suivi et le pilotage des procédés déployés dans ces usines nécessitent de nombreuses analyses générant de grandes quantités d'effluents radioactifs. Réduire les volumes mis en jeu lors de ces analyses permettrait donc de réduire la nocivité des échantillons et des effluents et donc d'accroitre la sureté pour le personnel et de réduire l'impact sur l'environnement et le coût de fonctionnement des usines. Parmi toutes les analyses effectuées, la mesure d'acidité libre est la plus fréquente, car c'est un paramètre indispensable pour pouvoir piloter correctement le procédé. C'est pourquoi, ces travaux de thèse ont abouti à l'amélioration de la méthode de mesure via une réduction d'échelle de l'analyse et une automatisation du protocole de mesure. Deux voies ont été étudiées : - le titrage par injection séquentielle (SIA), qui est un dispositif de 25 L de volume et qui par rapport à la méthode d'analyse de référence, réduit 1000 fois le volume d'échantillon nécessaire à l'analyse, 8 fois le temps d'analyse et 40 fois le volume d'effluents générés. - le titrage ballist-mix emploie un dispositif microfluidique qui, après intégration et réduction des composants, peut atteindre un volume de 25 mL et offre des performances analytiques comparables à celles obtenues en SIA. La méthode par SIA a été validée sur des solutions chargées en uranium alors que la technologie utilisée pour développer les titrages ballist-mix est en cours de validation. Cependant le principe opératoire du titrage ballist-mix est plus avantageux puisqu'il simplifie le travail de développement analytique du fait de la possibilité de simuler en avance les phénomènes physicochimiques ayant lieu lors du titrage / A joint study between the CEA and Areva La Hague has shown that chemical analysis is a crucial parameter for achieving a better performance in present and future spent nuclear fuel reprocessing plants. In fact, each plant’s process monitoring and control require a significant amount of laboratory analysis leading in overall to a considerable amount of nuclear waste. Hence, reducing the sample’s required volume for analysis would reduce its toxicity and subsequent waste, therefore increasing personnel safety, decreasing the environmental impact and the plant’s operation cost. Among the process control analytical workload, the free acidity measurement has been identified as a key analysis due to its measurement frequency. For this reason, the main objective of this research has been focused in the improvement of a reference method for free acidity measurement. The following work has been divided in two main studies seeking for the reduction of the sample volume and the automation of the analytical method protocol: - Sequential Injection Analysis (SIA) titration, whose application requires the employment of a device occupying a 25 L space, and which reduces 1000 fold the sample volume per analysis, 8 times the analysis time and 40 fold the amount of waste generated when compared to the reference analytical method. - Ballist-mix titration, whose analytical performance is equivalent to the SIA titration, but whose implementation is done inside a microfluidic device occupying a volume as low as 25 mL after integration of all of the elements needed for analysis. At the present time, the SIA titration has been validated using nitric acid samples containing uranyl cations, whereas the ballist-mix titration is being validated with the same sample conditions. However, this last analytical technique features a simplified operating principle which allows the user to shorten the analytical development process by opening the possibility to simulate the process before any experimentation

Analysis of the molecular speciation of organic compounds in solution is essential for the understanding of ionic complexation. The Raman spectroscopic technique was chosen for this purpose because it allows the identification of compounds in different states and it can give information about the molecular geometry from the analysis of the vibrational spectra. In this research the ionisation steps of relevant pharmaceutical material have been studied by means of potentiometry coupled with Raman spectroscopy; the protonation and deprotonation behaviour of the molecules were studied in different pH regions. The abundance of the different species in the Raman spectra of aqueous salicylic acid, paracetamol, citric acid and salicylaldoxime have been identified, characterised and confirmed by numerical treatment of the observed spectral data using a multiwavelength curve-fitting program. The non-destructive nature of the Raman spectroscopic technique and the success of the application of the multiwavelength curve-fitting program demonstrated in this work have offered a new dimension for the rapid identification and characterisation of pharmaceuticals in solution and have indicated the direction of further research. The work also covers the formation of novel cocrystal systems with pharmaceutically relevant materials. The existence of new cocrystals of salicylic acid-nicotinic acid, DLphenylalanine , 6-hydroxynicotinic acid, and 3,4-dihydroxybenzoic acid with oxalic acid have been identified from stoichiometric mixtures using combined techniques of Raman spectroscopy (dispersive and transmission TRS), X-ray powder diffraction and thermal analysis. Raman spectroscopy has been used to demonstrate a number of important aspects regarding the nature of the molecular interactions in the cocrystal. Cocrystals of salicylic acid - benzamide, citric acid-paracetamol and citric acid -benzamide have been identified with similar analytical approaches and structurally characterised in detail with single crystal X-ray diffraction. From these studies the high selectivity and direct micro sampling of Raman spectroscopy make it possible to identify spectral contributions from each chemical constituent by a peak wavenumber comparison of single-component spectra (API and guest individually) and the two- component sample material (API/guest), thus allowing a direct assessment of cocrystal formation to be made. Correlation of information from Raman spectra have been made to the X-ray diffraction and thermal analysis results. Transmission Raman Spectroscopy has been applied to the study cocrystals for the first time. Identification of new phases of analysis of the low wavenumber Raman bands is demonstrated to be a key advantage of the TRS technique.

Groundnuts (Arachis hypogaea L.) are an important subsistence and cash crop for smallholder farmers in Southern Africa. They require well drained light textured soils. However, most light textured soils are acidic and inherently infertile, and therefore require supplementary nutrients and amelioration with lime. In addition to application of a basal fertilizer, groundnut production also requires Ca. This increases the inputs required to produce the crop, particularly for smallholder farmers. The study examined two options for smallholder farmers, outside the classical lime application, for ameliorating soil acidity, i.e., evaluating the response of different groundnut genotypes for tolerance to soil acidity and low-cost liming alternatives. Initially ten groundnuts genotypes were screened for tolerance to soil acidity. Following this, three genotypes classified as tolerant and susceptible were used to evaluate the effect of high acid saturation on germination, emergence and seedling establishment. Thereafter, selected cultivars were used to compare calcium silicate, as an alternative to dolomitic lime, for ameliorating soil acidity and supplying calcium to developing pods. All three studies were conducted under controlled conditions: 25 ± 5°C and 20 ± 3°C day/night temperatures, 65% RH. Results measured as plant height, leaf area, yield, concentration and uptake of selected macro-and micro-nutrients showed that different groundnut genotypes differed in their response to soil acidity. Genotypes like Billy, Selmani, Rambo and JL 24 had low Al uptake and high Ca and P uptake and were classified as tolerant to acidity. In addition, these genotypes also had a higher leaf area and high number of nodules compared with Anel, Harts, Sellie, RG 784 and Robbie. With the exception of JL 24 all other tolerant genotypes (Billy, Selmani and Rambo) were large seeded. In the early establishment stage especially, root development was susceptible to soil acidity, but Rambo appeared to perform better than Jasper and Harts. Calcium silicate reduced soil acid saturation and provided enough calcium for pod development, suggesting that it may be used as an additional source of calcium. Soil acidity increased grain protein concentration and reduced its oil content, however, amelioration with either lime source reversed this trend. Thus, growing groundnuts in acid soils has implications for the commercial value of the product in terms of oil or protein supply. Overall, the study suggests that a combination of application of a cheap liming source like calcium silicate and growing tolerant cultivars, like Rambo, Billy and JL 24 might provide a window of opportunity for smallholder farmers to produce groundnuts possibly with only a fraction of the costs associated with ameliorating soil acidity. / Thesis (M.Sc.Agric.)-University of KwaZulu-Natal, Pietermaritzburg, 2011.

Le travail de thèse effectué a porté sur l'applicabilité et la compréhension d’un système catalytique bifonctionnel acide et hydro/déshydrogénante sur l'hydroconversion et l’hydrotraitement d'un Résidu Sous Vide. En amont de ce travail, il est rappelé qu'au-delà de 400 °C (régime thermique), la forte conversion du RSV conduit à des phénomènes indésirables de précipitation et d’instabilité, liés à l'augmentation de la polarité des asphaltènes. L’objectif de la thèse était donc de favoriser les réactions de craquage et d’hydrogénolyse à plus faible température (370 °C), grâce à la fonction acide du catalyseur, et d’étudier la nature des structures asphalteniques résultantes. Des catalyseurs modèles, de formulation NiMo, supportés sur des aluminosilicates préparés par greffage de silicium à la surface d'une alumine, ont été utilisés. Ces catalyseurs développent une acidité faible, apportée par le support. Cette acidité a été quantifiée et caractérisée sur les aluminosilicates synthétisés, comme sur le catalyseur fini. La phase hydrogénante, ainsi que la texture des solides, ont aussi été caractérisées en détail. Des catalyseurs, dont les trois paramètres précités ont pu être modifiés indépendamment, ont ainsi été obtenus.Les performances catalytiques ont ensuite été évaluées en hydroconversion d’un RSV Safaniya, en réacteur batch. Les résultats révèlent un impact limité de l’acidité sur les grandeurs globales du test. Les modifications successives des phases hydrogénantes, et l’apport de macroporosité, n’ont pas permis d’améliorer cet impact par la suite. L’analyse détaillée conduite sur les asphaltènes après conversion a mis en relief des modifications de structures moléculaires nettes. Celles-ci ont pu être illustrées via une méthode de reconstitution moléculaire. L'introduction d’acidité a ainsi favorisé les réactions de craquage des chaines aliphatiques ou naphténique des asphaltènes, sans pour autant augmenter l'aromaticité de la molécule. / The aim of this work was to study and investigated bifunctional sulfided and acidic catalyst for the hydroconversion and the hydrotraitment of a Vacuum Residue. Upstream works have already demonstrate that high level of residue conversion, at high temperatures ( > 400 °C), leads to create carbonaceous sediments (sediments), link to asphaltenes polarity and aromaticity. Thus, our objective was to promote hydrocracking reactions at lower temperatures (370 °C), by enhancing acidity of conventional sulfided catalysts. Structures of consequent asphaltenes, modified by acidity, were also studied. Model NiMo catalysts were obtained by grafting silica on the surface of alumina carriers. Characterization on carriers and sulfided catalysts reveal the improvement of a weak acidity. Hydrogenating phase and textures properties have also been characterized in this work. In the end, we have obtained catalysts with same texture, same hydrogenating power, but also different level of acidity strength. Catalytic performances were evaluated in batch reactor, for the hydroconversion reaction of a Safaniya Vacuum Residue. Results reveal no changes in hydroconversion or hydrotraitment reactions parameters with acidity. No improvement was observed by enhancing the hydrogenating power or by adding macroporosity on textures with acidic sulfided catalysts. Nonetheless, combinated asphaltenes analysis and molecular reconstructions methods have shown that acidity can modify asphaltènes structures and properties. Acidity enhances cracking reactions of aliphatic chains and naphthenic units, without improving the aromaticity of the molecules.

Solos ácidos cobrem cerca de 30% das áreas agricultáveis do mundo. Nestes solos, geralmente ocorrem baixas concentrações de cátions como cálcio e magnésio, enquanto a acidez (pH <5,5) promove a solubilização de Al3+. A exposição de raízes a pH ácido e/ou ao Al3+ inibe o crescimento radicular, reduz a viabilidade de células do ápice, promove estresse oxidativo, e pode causar desarranjos na parede celular. Na parede, é provável que tanto o H+ como o Al3+ atuem sobre a pectina, comprometendo a sua estrutura e funcionalidade. Por outro lado, peroxidases classe III (GPOX) parecem desempenhar um papel central nas modificações da parede celular, são induzidas por H+ e Al3+ e algumas isoformas são associadas à pectina. O objetivo deste trabalho foi caracterizar as respostas radiculares da cultivar Micro-Tom de tomateiro (Solanum lycopersicum L.) à toxidez por H+ e Al3+ e avaliar a capacidade do cálcio e do boro em aliviar esta toxidez com relação à inibição do crescimento radicular, queda na viabilidade celular e alterações na atividade de GPOX. Em raízes expostas a pH 4,0, após 30 min já foi possível observar a redução na viabilidade de células do ápice, avaliada através da absorção de azul de Evans. Observou-se elevação significativa na atividade de GPOX após 2 h de tratamento a pH 4,0. Apesar da defasagem na sua indução em relação à queda na viabilidade celular, a atividade de GPOX parece ser um melhor indicador da ação de H+. O uso do inibidor da GPOX (SHAM; ácido salicilhidroxâmico) indicou que estas enzimas desempenham um papel no sentido de impedir maiores danos às células por pH baixo. O cálcio (10 mM) aliviou totalmente a toxidez por H+ (pH 4,0 e 4,5) e Al3+ (10 ?M) em relação a crescimento radicular e viabilidade celular. O boro (30 ?M) aliviou totalmente a toxidez por H+ e Al3+ em relação a viabilidade celular, mas aliviou apenas parcialmente ou em nada a inibição do crescimento radicular por H+ ou Al3+, respectivamente. Tanto o cálcio quanto o boro suprimiram totalmente a indução da atividade de GPOX. O cálcio e o boro apresentaram interação positiva sobre o crescimento radicular a pH 5,8 e 4,5, mas não na presença de Al3+ e nem em relação à viabilidade celular ou atividade de GPOX. De modo geral, encontrou-se boa correlação entre viabilidade celular e atividade de GPOX. Tomado no seu conjunto, os dados evidenciam um papel importante de GPOX na toxidez por H+ e Al3+ e sugerem que, apesar de distintos, a toxidez por estes íons possivelmente apresentam alguns aspectos e mecanismos em comum. Também corroboram outros trabalhos que evidenciam a ação destes íons sobre a parede celular, em particular a matriz péctica. Estudos futuros deverão examinar se a GPOX que é induzida por H+ e Al3+ está associada à pectina da parede. / Acid soils cover about 30% of the arable land in the world. These soils usually have low concentrations of cations, such as calcium and magnesium, whereas the low pH (pH <5.5) increases the solubility of Al3+. Exposure of roots to low pH and/or Al3+ inhibits root growth, reduces cell viability of the root apex, promotes oxidative stress, and can cause derrangements in the cell wall. It is likely that both H+ and Al3+ act on pectin of the cell wall, affecting its structure and functionality. On the other hand, class III peroxidases (GPOX) appear to play a role in modifications of the cell wall, are induced by H+ and Al3+ and some isoforms are associated with pectin. The aim of this study was to characterize the responses of roots of the Micro-Tom cultivar of tomato (Solanum lycopersicum L.) to the toxicity of H+ and Al3+ and evaluate the ability of calcium and boron to alleviate this toxicity with respect to inhibition of root growth, decrease in cell viability and changes in the activity of GPOX. In roots exposed to pH 4.0, after 30 min it was already possible to observe a decrease in cell viability at the apex, as assessed by the uptake of Evans blue. We observed a significant increase in GPOX activity after 2 h of treatment at pH 4.0. Despite the lag in their induction in relation to the decrease in cell viability, GPOX activity seems to be a better indicator of the action of H+. The use of inhibitors of GPOX activity indicates that these enzymes play a role in preventing further damage to cells by low pH. Calcium (10 mM) completely alleviated H+ (pH 4.0 or 4.5) and Al3+ (10 mM) toxicity with respect to root growth and cell viability. Boron (30 mM) completely alleviated H+ and Al3+ toxicity with respect to cell viability, but only partly alleviated or had no effect on the inhibition of root growth by H+ or Al3+, respectively. Both calcium and boron completely suppressed the induction of GPOX activity. Calcium and boron displayed a positive interactive effect on root growth at pH 5.8 and 4.5, but not in the presence of Al3+ and not in relation to cell viability or GPOX activity. In general, good correlations were found between cell viability and GPOX activity. Taken together, the data indicate a significant role of GPOX activity in the toxicity of H+ and Al3+ and suggest that although different, the toxicity of these ions possibly share some common aspects and mechanisms. The data also corroborates other studies that indicate the cell wall as a target of toxicity, particularly the pectic matrix. Further studies should examine whether GPOX activity, which is induced by H+ and Al3+ is associated with pectin in the wall.

Thesis (MTech (Agriculture))--Cape Peninsula University of Technology, 2018. / Zinc deficiency on various soil types have been reported in arable soils of sub Saharan Africa (SSA) including South Africa. A pot trial was conducted at the Cape Peninsula University of Technology, Wellington campus to investigate the interaction of different application rates of Zn at various soil pH on the grain yield and quality of spring wheat in a completely randomized factorial design replicated three times. The four soil pH tested were: pHA: 5.1, pHB: 5.6, pHC: 6.1, pHD: 6.6 which correspond to lime application at 0, 0.5, 1 and 1.5 t/ha. Five Zn rates (Zn1: 3.5; Zn2: 4.5; Zn3: 5.5 Zn4: 6.5, and Zn5: 7.5 mg /kg soil which correspond to Zn1: 7; Zn2: 9; Zn3: 11; Zn4: 13 and Zn5: 15 kg /ha) were applied at two (planting and flowering) growth stages. Yield and yield component data collected were analyzed using SAS version 9.2 and means were separated by Duncun’s Multiple Range Test (DMRT). The results showed that grain yield and yield components were significantly affected by lime application pHC (6.1): 1t/ha at planting. Zn application at planting had no significant effect on the grain yield and yield components. However, at flowering, the simultaneous increase of Zn along with increase in lime positively affected grain yield and yield components. Plant analysis showed that at both stages (planting and flowering), Zn application, especially at pH 6.6, significantly increased P, K, Ca, Na, Mg Fe, Cu and B concentrations in wheat grain, but the concentrations of N, Mn, Zn and protein remained unaffected. Zn application had no effect on most nutrients due to the presence of lime. While the absence of lime, Zn4: 6.5mg/kg (corresponding to 13kg/ha) significantly increased the nutrients. In addition, Zn3: 5.5mg/kg (corresponding to 11kg/ha) promoted Zn absorption by grain in all treatments.

Os lodos de curtume apresentam elevados teores de nutrientes e potencial de neutralização da acidez do solo, possibilitando sua utilização em áreas agrícolas, como uma alternativa para disposição e reciclagem desses resíduos. Por outro lado, o acúmulo no solo de altas concentrações de alguns elementos, como nitrogênio, sódio e cromo, provenientes dos lodos de curtume, podem proporcionar impactos negativos ao meio ambiente. Como os microrganismos desempenham função importante na sustentabilidade do solo e nutrição vegetal e respondem prontamente a alterações ambientais, torna-se importante estudar o impacto da utilização em conjunto do lodo do caleiro e lodo primário da ETE (com teor reduzido de cromo) sobre os atributos biológicos do solo. No presente trabalho avaliaram-se os atributos microbiológicos do solo em um experimento de campo instalado em Rolândia (PR), com a aplicação de doses de lodo de curtume (0, 3,4, 13,5, 23,6 e 33,7 Mg ha-1 em 2006 e 0, 2,3, 9,0, 15,8 e 22,6 Mg ha-1 em 2007) baseadas no teor de N total do lodo, com doses equivalentes entre 0 e 1200 kg ha-1 de N total. O delineamento experimental foi o de blocos completos casualizados com quatro repetições. A aplicação de lodo de curtume alterou a estrutura genética de bactérias, principalmente logo após cada aplicação do resíduo. Os tratamentos que receberam lodo apresentaram comunidade bacteriana diferenciada daquela do tratamento controle. Verificou-se que o efeito do lodo sobre essas populações é mais prolongado no primeiro ano de aplicação, com efeitos ainda evidentes após 300 dias da aplicação. No segundo ano da aplicação, não houve diferença nas comunidades bacterianas entre as menores doses e o controle após 260 dias da aplicação. O mesmo resultado foi observado para a atividade biológica do solo. Os atributos mais influenciados pela aplicação do resíduo foram as atividades da asparaginase e urease. Os resultados mostram que a alteração da estrutura da comunidade microbiana tem relação direta com as modificações na atividade biológica desse solo. A densidade de esporos de fungos micorrízicos arbusculares (FMA) diminuiu com o aumento das doses de lodo de curtume. A taxa de colonização radicular foi alta (64%), mas sem efeito significativo da aplicação de lodo. Foram encontradas 18 espécies de seis gêneros de FMA (Acaulospora, Glomus, Gigaspora, Scutellospora, Paraglomus e Ambispora). Houve queda na diversidade e modificação nas frequências relativas dos FMA nas maiores doses de lodo, assim como, o lodo de curtume alterou a composição de espécies de FMA, modificando a condição micorrízica desse solo. Altas doses de lodo de curtume também alteraram a estrutura da comunidade microbiana baseada no perfil de ácidos graxos de fosfolipídios (PLFA). O consumo de substratos de carbono pela comunidade microbiana foi acelerado e intensificado pela aplicação do resíduo, mostrando que o potencial metabólico dessa comunidade foi diferente do tratamento que não recebeu o resíduo. As alterações observadas nos atributos microbiológicos estão relacionadas às modificações nos atributos químicos do solo, decorrentes da aplicação do lodo de curtume, principalmente ao aumento do teor de N inorgânico e à elevação do pH do solo. / Tannery sludge is a residue with a high content of nutrients and soil acidity neutralization power, which allow its use in agricultural areas and could be an advantageous alternative for its final disposal and recycling. Furthermore, the accumulation in soil of high concentrations of certain elements, such as nitrogen, sodium and chromium, typically present in tannery sludge can provide negative impacts on the environment. Microorganisms play a very important role in soil sustainability and plant nutrition, as well as, respond quickly to environmental changes. Thus, it becomes important to study the impact of a material resulting of the mixture of sludge from the liming process and the primary sludge from the wastewater treatment plant, with a low level of chromium, on soil biological attributes. This study aimed to evaluate the microbial soil attributes after application of tannery sludge doses (0, 3,4, 13,5, 23,6, and 33,7 Mg ha-1 in 2006 and 0, 2,3, 9,0, 15,8, and 22,6 Mg ha-1 in 2007) based on total N content of sludge, with doses equivalent to 0 up to 1200 kg ha-1 total N. Tannery sludge application modified the genetic structure of the bacterial community mainly right after each sludge application. There was a clear separation between the bacterial communities in different treatments, being that each dose of sludge imposed a specific community different from the control. It was verified that the effect of sludge on these bacterial populations is more extended in the first year of application, when the effect remained until after 300 days of application. In the second year of sludge application, there was no difference in the bacterial community among the smallest doses and the control after 260 days of the application. The same result was observed regarding soil biological activity. The most influenced properties by the application of tannery sludge were asparaginase and urease activities (both are related to the N cycle). Changes in the structure of the bacterial community were directly related to changes of biological activity in this soil. The AMF spore density decreased with increasing doses of tannery sludge. The rate of AMF root colonization was high (64%) and stayed unaffected by the sludge. Eighteen AMF species belonging to six genera (Acaulospora, Glomus, Gigaspora, Scutellospora, Paraglomus and Archaeospora) were recorded. At the highest doses of sludge we observed decreased AMF species diversity and changes in their relative frequencies. Furthermore, the tannery sludge altered AMF species composition, modifying the mycorrhizal status of this soil. High doses of tannery sludge modified the microbial community structure based on the phospholipids fatty acids (PLFA) profile. The carbon substrate consumption by the microbial community was accelerated and intensified by sludge application, showing that the metabolic potential of this community was different from that of the control. The changes observed in the microbial attributes are related to modifications in the soil chemical attributes, mainly to the increases of inorganic N and soil pH.

Submitted by Eunice Novais (enovais@uepg.br) on 2018-05-21T17:38:07Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Maghnom Henrique Melo.pdf: 1072311 bytes, checksum: 79acf6922562d6c4ef1679b5c261162c (MD5) / Made available in DSpace on 2018-05-21T17:38:07Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Maghnom Henrique Melo.pdf: 1072311 bytes, checksum: 79acf6922562d6c4ef1679b5c261162c (MD5) Previous issue date: 2018-02-23 / Dentro do atual contexto energético mundial, é crescente a discussão sobre fontes alternativas e renováveis às fontes tradicionais e fósseis de energia. No Brasil, vale destacar a adoção de biocombustíveis em motores de combustão interna, como a utilização do biodiesel como alternativa na substituição de petrodiesel, que é derivado do petróleo. Como existem inúmeras cultivares de soja utilizadas no Brasil, faz se necessário caracteriza-las para teor de óleo e proteína, a fim de auxiliar a indústria na tomada de decisão de quais materiais adquirir de acordo com as finalidades de produção (óleo ou farelo de soja) e também propiciar ao produtor obter valor diferenciado para o seu produto, aumentando os lucros deste. Objetivou-se determinar valores qualitativos e quantitativos dos grãos de diferentes cultivares de soja O delineamento experimental utilizado foi em blocos aleatorizados. Os tratamentos consistiram em 12 cultivares: NS 5959 IPRO®, NS 6906 IPRO®, M 5705 IPRO®, M 6410 IPRO®, BRS 1003 IPRO®, BRS 1001 IPRO®, FTR 2155 RR®, TMG 7062 IPRO®, TMG 7262 IPRO®, BS 2606 IPRO®, Brasmax Garra IPRO® e 96Y90®. O experimento foi instalado no município de Ponta Grossa, estado do Paraná, safra 2016/17. Foi realizado extração a quente do óleo utilizando um hidrocarboneto como solvente (hexano) em aparelho do tipo Soxhlet. A determinação do índice de acidez foi feita através de titulação de amostra com solução aquosa de hidróxido de potássio. A densidade do óleo foi determinada através de densímetro digital na temperatura de 20º C. O teor de proteína foi determinado pelo método de digestão semi-micro-Kjeldahl. Concluiu-se que o índice de acidez do óleo, variou de 1,6 a 15,7 mg KOH g-1 de óleo e a densidade do óleo variou de 915 a 921 kg m-3 entre as cultivares. O teor de óleo dos grãos de soja e de proteína variou de 156 a 179 g de óleo kg-1 de massa de grãos e de 336 a 291 g de proteína kg-1 de grãos, respectivamente. Das variáveis analisadas não houve diferenças significativas entre as cultivares para teor de óleo e de proteína, houve três cultivares com índice de acidez do óleo acima do aceitável pela indústria e a densidade do óleo de todas as cultivares estudadas ficaram acima do limite inferior estabelecido por normas. / Within the current global energy context, the discussion on alternative and renewable sources to traditional sources and fossil fuels is growing. In Brazil, it is worth mentioning the adoption of biofuels in internal combustion engines, such as the use of biodiesel as an alternative in the substitution of petrodiesel, which is derived from petroleum. As there are numerous soybean cultivars used in Brazil, it is necessary to characterize them for oil and protein content, in order to assist the industry in making the decision of which materials to acquire according to production purposes (soy oil or soybean meal) and also provide the producer with differentiated value for their product, increasing their profits. The objective was to determine the oil acidity and density index, oil and protein content of soybean grains extracted from different cultivars in the Campos Gerais region. The experimental design was randomized blocks. The treatments consisted of 12 cultivars: NS 5959 IPRO®, NS 6906 IPRO®, M 5705 IPRO®, M 6410 IPRO®, BRS 1003 IPRO®, BRS 1001 IPRO®, FTR 2155 RR®, TMG 7062 IPRO®, TMG 7262 IPRO®, BS 2606 IPRO®, Brasmax GARRA IPRO® and 96Y90®. The experiment was installed in the municipality of Ponta Grossa, state of Paraná, harvest 2016/17. Hot oil extraction was performed using a hydrocarbon solvent (hexane) in Soxhlet type apparatus. The determination of the acid number was done by titrating the sample with aqueous solution of potassium hydroxide. The density of the oil was determined by a digital densimeter at a temperature of 20º C. The protein content was determined by the semi-micro-Kjeldahl digestion method. The measured variables were submitted to F and Scott-Knott tests, with a confidence level higher than 95% of probability. The acid value of the oil varied from 1.6 to 15.7 mg KOH g-1 of oil and the oil density ranged from 915 to 921 kg m-3 between the cultivars. The oil content of the soybean and protein grains ranged from 156 to 179 g of oil kg-1 of grain mass and 336 to 291 g of kg-1 of grain protein, respectively. Of the analyzed variables there were no significant differences between the cultivars for oil and protein content, there were three cultivars with an oil acid value above the industry acceptable and the oil density of all cultivars studied were above the lower limit established by standards .

Depuis la domestication du pommier, l’homme a progressivement sélectionné des variétés plus performantes, notamment pour la qualité du fruit, la productivité ou la résistance aux pathogènes. Les bases génétiques de ces caractères ont été explorées par cartographie en descendances F1 ne permettant d’explorer qu’une infime partie de la diversité génétique disponible.L’objectif de la thèse portait sur l’analyse des bases génétiques de caractères de qualité du fruit et de résistance du pommier à la tavelure et au feu bactérien dans des collections représentant une diversité plus large. Le génotypage de core collections de variétés anciennes s’est fait à l’aide de deux puces 8k et 480kSNPs ou grâce à du ré-séquençage de gènes. Des traces de différenciation génétique entre pommes à cidre et à couteau ont été identifiées et partiellement reliées à la voie des polyphénols. Après analyse de l’étendue du déséquilibre de liaison à large et fine échelle, une approche de génétique d’association a permis l’identification de régions génomiques associées à la variation de plusieurs caractères de qualité du fruit, dont le haut du groupe de liaison 16 rassemblant l’acidité (locus Ma), la fermeté, la jutosité et l’amertume (gène LAR). Pour la résistance au feu bactérien, une région contenant un homologue du gèneNPR1 (activateur de défenses) a été identifiée.Cette thèse a ainsi permis de préciser la localisation potentielle de QTLs identifiés préalablement par cartographie génétique et d’identifier de nouvelles ressources utiles dans de futurs programmes de sélection assistée par marqueurs. / Since apple domestication, humans have progressively selected improved varieties, especially for traits linked with fruit quality, productivity or resistance to pathogens. The genetic bases underlying these traits have been explored thanks to genetic mapping in F1 segregating populations that only allows the study of a small part of the available genetic diversity. The aim of this work was to analyze the genetic bases of fruit quality and disease resistance against apple scab and fire blight, in collections of old apple varieties representing a much larger diversity. Genotyping of core collections was performed either with arrays of 8k and 480k SNPs or by resequencing of chosen genes. Signs of genetic differentiation were identified between cider and dessert apples and were partially linked to the polyphenols pathway. After studying linkage disequilibrium, both on a large and a small scale, an association genetics approach allowed the identification of genomic regions associated with the variation of several fruit quality traits. Especially, the top of linkage group 16 was found to be linked with acidity (locus Ma), firmness, juiciness and bitterness (LAR gene). Concerning the resistance of apple to fire blight, a region containing a homolog of the NPR1 gene (defense activator) was identified. This thesis allowed the refining of the putative localization of previously identified QTLs and the identification of new genetic resources that could be useful in future selection programs using marker assisted selection.

Ce travail porte sur la compréhension des paramètres du catalyseur (texture, effet de support) permettant d’améliorer la réaction de conversion de liquéfiats de charbon. En effet, le catalyseur actuellement employé est un catalyseur du type conversion de résidu sous vide de brut de pétrole. Or ces matrices sont différentes en termes de poids moléculaires et de teneur en hétéroélément (O et N). Pour atteindre l’objectif de cette thèse, une caractérisation poussée du liquéfiat a été menée à l’aide de diverses techniques (GCxGC, HR-13C-RMN, FT-ICR/MS,…). Cette analyse détaillée du liquéfiat a mis avant son caractère fortement aromatique. Les extractions aux solvants ont permis d’isoler les asphaltènes et préasphaltènes de ce liquéfiat. Leurs analyses montrent que ces familles de composés sont de plus faible masse moléculaire que les asphaltènes des résidus pétroliers, et que leur teneur en hétéroélément est plus importante. Les tests catalytiques de conversion de liquéfiat ont été réalisés à 420°C 15MPa d’H2 pendant 8h. Ils montrent que l’augmentation de la taille de pore (mésoporeux) ainsi que l’apport d’une bimodalité du support (méso+macroporosité) permettent d’augmenter le transfert de matière et donc d’augmenter le coefficient de diffusion ce qui a pour conséquence d’améliorer le rendement en produits plus légers. Concernant la nature du support, de part sa capacité à favoriser les réactions d’HDO le TiO2 (vs Al2O3) permet de limiter la compétition entre les composés oxygénés et les composés hydrocarbonés. En conclusion, ce travail montre que plusieurs paramètres sont susceptibles d’améliorer les performances des catalyseurs de conversion des liquéfiats de charbon / This work focuses on the comprehension of the catalyst parameters (textural properties and support effect) that increase the yield of the coal liquid upgrading. The current in use catalyst was design for the petroleum vacuum residue conversion. However, these two feeds present different characteristics such as the average molecular weight and the amount of heteroelement (especially O and N). To reach our goal, an in-depth characterization of the coal liquid was carried out using techniques such as GCxGC, HR-13C-NMR, FT-ICR/MS. This coal liquid analysis pointed out its strong aromatic character. Extractive solvent experiments isolated the asphaltenes and preasphaltenes and their analysis show that they have a smaller average molecular weight distribution than that of petroleum asphaltenes. Catalytic experiments were carried out at 420°C, 15MPa of H2 for 8h. It shows that the increasing mesoporous size and the bimodality (meso + macroporosity) enable to raise the mass transfer thus the diffusion coefficient which enhances the yield in lighter products. The capability of TiO2 (as a support vs Al2O3) to promote HDO reaction, enables to restrain the competition between oxygen containing compounds and pure hydrocarbons. To conclude, this work demonstrates that several parameters can enhance catalyst’s performance for the coal liquid upgrading