Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Cette étude a pour objectif l'étude des processus impliqués dans la production de l'acrylate de 2-éthylhexyle, ester gras dérivé de l'acide acrylique. Cette réaction est accélérée par l'emploi d'un catalyseur solide, une résine acide sulfonée. Les interactions spécifiques des différents composés avec cette résine ont été étudiées à température ambiante. A 90°C, le couplage avec la cinétique de réaction a été analysé et modélisé en réacteur fermé. Un montage pilote spécifique conçu au laboratoire a permis la réalisation de réactions dans un réacteur en lit fixe, dont la structure tripartite permet le suivi des concentrations liquides dans le montage. Une modélisation représentant cette installation a été mise au point, associant l'affinité sélective, la cinétique de réaction et l'hydrodynamique de l'écoulement. Ce modèle a ensuite été utilisé pour l'analyse de modèles de tendances, pour déterminer des conditions de fonctionnement améliorés d'un procédé de taille industrielle / This study aims at analyzing and understanding the processes involved in the production of 2-ethylhexyl acrylate. This fatty ester is a derivative of acrylic acid. This reaction is accelerated by the use of a solid catalyst, a sulfonated resin acid. The specific interactions of compounds with this resin were studied at room temperature. At 90°C, the coupling of kinetics and selective affinity was analyzed and modeled in a closed reactor. A specific pilot installation was designed in laboratory. Esterification reactions were performed. in this fixed bed reactor. The tripartite structure allows the monitoring of liquid levels in all installation. A model representing this system was developed, involving selective affinity, kinetics and hydrodynamic. This model was then used to analyze trends models to determine improved operating conditions for an industrial size process

Le cadmium (Cd) est un élément trace présent dans les sols agricoles qui contamine la chaîne alimentaire en étant prélevé par les plantes et accumulé dans les produits végétaux consommés. La biodisponibilité du Cd est un concept au cœur de l’évaluation des risques de transfert excessif du Cd du sol vers les plantes. Les plantes prélevant essentiellement l’ion Cd2+ dans la solution de sol, la biodisponibilité est fonction de deux principaux processus, la spéciation du Cd en solution (les différentes formes chimiques prises par le Cd en solution) et le partitionnement du Cd2+ entre la phase solide et la solution. L’objectif principal de ce travail a été d’élaborer des modèles simples à visée opérationnelle prédictifs de la concentration en Cd2+ dans la solution de sols agricoles, en modélisant soit la spéciation du Cd en solution de sol, soit le partitionnement phase solide-solution du Cd2+, celui-ci permettant de renseigner en outre la capacité de la phase à réapprovisionner la solution de sol lors de l’absorption racinaire. Nous avons également recherché des modèles pour la prédiction des teneurs en Cd2+ retrouvées dans les grains de blé dur. Nous avons développé deux approches de modélisation. La première, statistique, permet de produire des modèles simples à visée opérationnelle. La seconde, géochimique, permet de comprendre les mécanismes dominants et donc de juger de la cohérence de modèles statistiques simples pour représenter des processus physico-chimiques complexes. Ces deux approches ont montré de manière cohérente que pour les sols agricoles faiblement contaminés, le Cd qui s’échange entre la phase solide et la solution est vraisemblablement sorbé faiblement et peut-être estimé par le Cd extrait par NH4NO3 1 M minoré par une fraction fixée à des oxydes de manganèse. Les modélisations ont également montré l’importance du pH et de la teneur en Ca en solution comme variables contrôlant la solubilité de Cd2+, probablement en raison de leur rôle à régir la disponibilité des sites de sorption et de complexation vis-à-vis du Cd. Le modèle statistique le plus performant pour prédire la teneur en Cd dans le grain de blé dur reprend également ces variables, suggérant ainsi que les modèles statistiques simples de prédiction de la spéciation en solution et de partitionnement sol-solution du Cd sont des modèles pertinents pour estimer la biodisponibilité et qu’ils peuvent permettre de classer des sols en fonction des risques de transfert du Cd du sol vers une culture. Par rapport à l’évolution du contexte réglementaire, le modèle statistique prédictif de la teneur en Cd dans le grain a montré par validation croisée qu’il pourrait discerner de façon assez fiable (88 %) des différences de 0.05 mg Cd.kg-1 de grain et que sa fiabilité serait moindre (65 %) pour des différences de 0.025 mg Cd.kg-1. / Cadmium (Cd) is a trace element found in agricultural soils which can contaminate the food chain by being taken up by plants and accumulated in consumed plant products. The bioavailability of Cd is a concept at the centre of the risk assessment of Cd transfer from soil to plants. Plants, taking up essentially the free form of Cd (Cd2+) in the soil solution, bioavailability is a function of two main processes, the Cd speciation in solution (the different chemical forms taken by the Cd in solution) and the partitioning of Cd2+ between the solid phase and the solution. The main objective of this work was to develop simple predictive operational models of Cd2+ concentrations in agricultural soil solution, by modelling either Cd speciation in soil solution or Cd2+ solid-solution partitioning, the latter to further inform the ability of the phase to replenish the soil solution during root absorption. We also looked for models for the prediction of Cd2+ levels found in durum wheat grains. We have developed two modelling approaches. The first, statistical, allows to produce simple models for operational purposes. The second, geochemical, allows to understand the dominant mechanisms and thus to judge the coherence of simple statistical models to represent complex physicochemical processes. These two approaches have consistently shown that for poorly contaminated agricultural soils, the exchanged Cd between the solid phase and the solution is likely to be weakly sorbed and can be estimated by the Cd extracted by 1M NH4NO3 minus a fraction attached to amorphous manganese oxides. Modelling also showed the importance of pH and Ca content in solution as variables controlling the solubility of Cd2+, probably because of their role in controlling the sorption site availability and Cd complexation. The best-performing statistical model for predicting Cd content in durum wheat also picks up these variables, suggesting that simple statistical models for speciation in solution and soil-solution partitioning of Cd are relevant models to estimate bioavailability and that they can be used to classify soils according to the risks of the transfer of soil Cd to a crop. Compared to the evolution of the regulatory context, the statistical model predictive of the Cd content in the grain shown by cross validation that it could discern relatively reliably (88%) the differences of 0.05 mg Cd.kg-1 of grain and that its reliability would be less (65%) for differences of 0.025 mg Cd.kg-1.

L'industrie nucléaire produit, de nos jours, une large gamme d'effluents radioactifs liquides contenant du césium. Les matériaux à base de cyanométallates présentent une très forte affinité pour l'incorporation de cet élément sur une grande plage de pH ainsi qu'une bonne résistance à l'irradiation ce qui les rend très intéressant pour la décontamination. Chaque année, à La Hague, plusieurs centaines de m3 d'effluents radioactifs sont traités par un précipité préformé de ferrocyanure de nickel massif (nommé PPFeNi, de formule générale K2xNi2-x[Fe(CN)6] avec 0,5>x>1,1). Cette technique présente de bons rendements de décontamination mais elle est lourde à mettre en œuvre et produit une boue qui se doit ensuite d'être traitée par les filières de déchets disponibles. L'objet de cette thèse est de trouver un matériau pour la décontamination du Cs à la fois efficace, sélectif, adapté au procédé de décontamination en continu (colonne) et compatible avec les déchets classiques (ciments ou verres). Pour atteindre ce but, nous avons plusieurs objectifs :i) L'étude de matériaux massif à base de cyanométallate afin d'améliorer les connaissances sur le mécanisme de fixation du césium sur ces composés en variant la nature du métal de transition et la présence ou non de potassium au sein de la structure cristalline,ii) La synthèse de nanocomposites contenant des nanoparticules de cyanométallates incorporées dans des matrices inorganiques de type silice mésostructurée et verre poreux. La silice est utilisée comme modèle, alors que le verre poreux mise en forme de bille sera utilisé en vue d'un procédé de décontamination. Les matériaux massifs à base de cyanométallate contenant du potassium dans la structure sont ceux qui possèdent la plus grande capacité de sorption vis-à-vis du Cs. Les matériaux hybrides contenant des nanoparticules de cyanométallates possèdent une capacité maximale absolue inférieure à celle des matériaux massifs respectifs, cependant rapporté à la quantité de particule sorbante, la capacité maximale de sorption des matériaux hybrides est supérieure à celle des massifs. En revanche, la sélectivité est comparable pour les matériaux hybrides et les matériaux massifs, avec un coefficient de distribution de l'ordre de 104 à 105 mL.g-1.Les performances des matériaux hybrides ont été évaluées sur des effluents réels. Ces matériaux semblent très prometteurs pour la décontamination d'effluents à partir d'un procédé de traitement en colonne puisqu'ils présentent d'une part une forte sélectivité vis-à-vis du césium et ce malgré une forte salinité de la solution à décontaminer et d'autre part une mise en forme (bille de verre) adaptée à ce type de procédé. / Nuclear industry produced, nowadays, a wide range of liquid radioactive waste containing cesium. Materials based on cyanométallates exhibit a very high affinity for the inclusion of this element in a wide range of pH and a good resistance to ionising radiation which makes them very interesting for decontamination. Every year, at La Hague, several hundred m3 of radioactive waste are treated by a nickel ferrocyanide preformed precipitate in bulk form (PPFeNi, general formula K2xNi2-x [Fe (CN) 6] with 0,5> x> 1,1). This process shows a good decontamination but it's difficult to implement and it produces a sludge that must then be treated by waste channel available.The purpose of this thesis is to find a material for the decontamination of Cs which have a good capacity, selectivity, adapted for continuous decontamination process (column) and compatible with conventional waste (cement or glass). To achieve this goal, we have several objectives:i) The study of solid materials based on cyanometallate to improve knowledge on the mechanism of fixation of cesium on these compounds by varying the nature of transition metal and the presence or not of potassium in the crystal structure,ii) Synthesis of nanocomposites containing cyanometallate nanoparticles incorporated into inorganic matrices which are mesostructured silica and porous glass. Silica is used as a template, whereas the porous glass shaping ball will be used for a decontamination process.Bulk materials containing potassium in the structure present the greater sorption capacity toward Cs. Hybrid materials containing cyanometallate nanoparticles have a lesser absolute capacity than the respective bulk materials, however, based on the amount of sorbent particles, the maximum sorption capacity of hybrid materials is higher than bulk materials. However, the selectivity is comparable for hybrid and bulk materials with a distribution coefficient about 104 to 105 mL.g-1.The performance of the hybrid materials were evaluated on real effluents. These materials are very promising for the decontamination of effluents from a treatment process in column one hand they have a high selectivity towards cesium and despite high salinity of the solution to decontaminate and other formatting (glass beads) adapted to this type of process.

A interação de elementos potencialmente tóxicos com solos e a caracterização quanto à mobilidade e potencial de liberação ao ambiente são importantes para avaliação de risco ambiental. No caso de solos altamente intemperizados, como os Latossolos, a interação pode ser diferenciada devido à elevada acidez, baixa densidade de cargas negativas, maiores quantidades de minerais de argila 1:1 e de (hidr)óxidos de Fe, Al e Mn, em que predominam cargas negativas variáveis com o pH. O objetivo nesta tese foi caracterizar a capacidade de sorção, a distribuição entre as frações do solo, a especiação temporal, a predição da capacidade de sorção e a dessorção com método dinâmico de extração de Cd(II) em seis solos tropicais, incluindo três Latossolos. Amostras dos seis solos foram utilizadas para avaliação da interação com Cd(II), utilizando extração sequencial e especiação por espectroscopia de absorção de raios-X próximo à estrutura da borda (XANES) para avaliação da cinética de sorção. Dados de 29 solos foram utilizados para desenvolvimento de modelo de regressão linear para predição das capacidades de sorção de Cd(II). A caracterização da dessorção de Cd por extração convencional e dinâmica foi feita em solos de textura médio-arenosa, argilosa e em um solo de referência certificado. Os resultados de sorção foram ajustados ao modelo de Langmuir. As capacidades de sorção e as energias livres padrão de Gibbs variaram de 37 à 1296 mg kg-1 e de -16,6 até -27,0 kJ mol-1, respectivamente. A sorção foi fraca e reversível, e mais de 90% do Cd estava sorvido como espécies disponíveis. A especiação temporal indicou evidências fracas e variáveis para as alterações químicas do Cd no solo, sugerindo que o elemento liberado nessas amostras se ligou à matéria orgânica do solo e aos óxidos minerais ou permaneceu dissolvido, com pequenas alterações na especiação nos meses seguintes. O modelo linear representou 98% dos resultados empíricos apenas em função de uma variável, que foi o ensaio de sorção simplificado com apenas uma concentração de Cd(II). Apesar de a capacidade de sorção prevista com o modelo ter apresentado variação de cerca de 20% em relação ao empírico, o modelo de predição apresenta potencialidade de aplicação para avaliações iniciais e rápidas. A dessorção avaliada em batelada e em fluxo indicou dessorção próxima de 100% nas frações que representam disponibilidade no ambiente, enquanto o sistema desenvolvido para extração dinâmica foi adequado na mistura das soluções com a amostra de solo e propiciou rápida troca de extratores. De modo geral os atributos do solo, bem como a classe, influenciaram, mas não definiram a interação do Cd(II) com o solo. Por sua vez, o Cd(II) incorporado ao solo apresenta grande risco ambiental e de interação com a biota / The interaction of potentially toxic elements in soils and characterization as mobility and potential of environmental release are important for environmental risk assessment. In the case of highly weathered soils, as Oxisols, interaction can be differentiated, due to the high acidity, low density of negative charges, and higher amounts of 1:1 clay minerals and Fe, Al and Mn (hidr)oxides, in which negative charges are variables with pH. The objectives in this thesis was to characterize the Cd(II) sorption capacity, distribution between soil fractions, temporal speciation, prediction of sorption capacity and desorption with dynamic extraction method in six tropical soils, including three Oxisols. Samples of the six soils were used to assess the interaction with Cd(II) using sequential extraction and the speciation with X-ray absorption near edge structure spectroscopy (XANES) to evaluate the adsorption kinetics. Data of 29 soils were used to develop a linear regression model for prediction of Cd(II) sorption capacity. The Cd desorption characterization trough conventional and dynamics extractions was performed in a medium-sandy, a clayey and a certified reference soils. The sorption results were fitted to the Langmuir model. Sorption capacities and standard Gibbs free energy ranged from 37 to 1296 mg kg-1 and from -16.6 to -27.0 kJ mol-1, respectively. Sorption was weak and reversible, and more 90% Cd was sorbed as available species. The temporal speciation indicated weak and variables evidence of chemical changes of Cd in the soil, suggesting that this element released in these soils bound to the soil organic matter and to mineral oxides or remained dissolved, with minor changes in speciation in the following months. The linear model accounted for 98% of empirical results only on the basis of a single variable, which was the sorption simplified experiment with only one Cd(II) concentration. Although the sorption capacity predicted with the model ranged about 20% of the empirical, prediction model has potential of application for initial and rapid assessments. The desorption evaluated in batch and flow indicated desorption of about 100% in the fractions representing availability in the environment, meanwhile the system developed for dynamic extraction was adequate to mix the solutions with the soil sample and provided rapid exchange of extractants. Overall, the soil characteristics and the class had influence, but did not define the interaction of Cd(II) with the soil. On the other hand, the Cd(II) incorporated into the soil has a great environmental risk and to interact with the biota

L'industrie nucléaire publique et militaire génère une quantité importante d'effluents liquides radioactifs qu'il faut traiter avant leur rejet dans l'environnement. Des procédés de décontamination alternatifs aux techniques industrielles (évaporation, traitement chimique) sont en cours de développement, comme par exemple le traitement en colonne ou le couplage filtration/sorption. Une partie des recherches associées à ces techniques de décontamination porte sur l'élaboration et la mise en forme de sorbants spécifiques. Dans ce contexte, les objectifs de cette thèse étaient d'une part d'étudier la synthèse en milieu CO2 supercritique (SC) de films de TiO2 déposés sur des supports macroporeux et d'autre part d'évaluer leur potentiel d'extraction dans ces procédés alternatifs. Une méthode de synthèse reproductible a été mise au point, basée sur la décomposition thermique de l'isopropoxyde de titane en milieu CO2 SC entre 150°C et 350°C. Dès 150°C, cette méthode permet la réalisation de films de TiO2 nanostructurés et adhérents sur des supports macroporeux en céramique (mousses, supports tubulaires en alumine α). L'effet de la température de synthèse de ces matériaux sur leurs caractéristiques physico-chimiques et leurs propriétés de sorption a été étudié sur des poudres de TiO2 élaborées dans les mêmes conditions que les films supportés. Les meilleures performances de sorption ont été observées pour la poudre obtenue à 150°C, du fait de sa plus grande densité de sites de surface par rapport aux poudres élaborée à 250°C et 350°C. Cette température de synthèse (150°C) a donc été sélectionnée pour l'étude détaillée des sorbants composites (TiO2/supports) afin d'évaluer leurs performances de sorption dans les procédés de traitement en continu. Les essais de sorption en colonne ont montré qu'une mousse en alumine macroporeuse (Φpore=400µm) revêtue de TiO2 est adaptée pour traiter des effluents en mode dynamique à fort débit. La taille des macropores et la hauteur de colonne sont des paramètres importants à maitriser. Pour le traitement par filtration/sorption, les membranes de TiO2 présentent une bonne résistance mécanique et sont capables d'extraire le strontium en mode dynamique. D'autre part dans le cas du strontium, les sorbants composites (TiO2/mousse ou TiO2/support tubulaire) sont régénérables à 100% à l'aide d'une solution aqueuse acidifiée (pH=3). / Public and military nuclear industry generates a significant amount of radioactive liquid waste which must be treated before being released into the environment. Decontamination methods alternative to the industrial techniques (evaporation, chemical treatment) are being developed, such as column treatments or coupled filtration/sorption processes. Current researches mainly focus on the development and shaping of specific sorbents. In this context, the objectives of this thesis were first to study the synthesis of TiO2 layers on macroporous ceramic supports in supercritical (SC) CO2 and then to evaluate their potential for radionuclide extraction in these alternative processes. A robust synthesis method has been developed, based on the thermal decomposition of titanium isopropoxide in SC CO2 in the temperature range between 150°C and 350°C. Nanostructured TiO2 films were formed on the macroporous supports (ceramic foams, tubular α-alumina supports) with good adhesion, already at 150°C. The effect of the synthesis temperature on sorbents physico-chemical characteristics and sorption properties has been studied with TiO2 powders prepared under the same conditions as the supported films. The best sorption performance were observed for the powder prepared at 150°C, owing to its higher density of surface sites in comparison with powders prepared at either 250°C or 350°C. Consequently, this synthesis temperature (150°C) was selected for a detailed study of the composite sorbents (TiO2/support), in order to assess their sorption performance in continuous treatment processes. The sorption experiments have shown that a column of alumina macroporous foam (Φpore = 400μm) coated with TiO2 was suitable for processing effluents in dynamic mode with high throughputs. Both macropore sizes and column height were revealed as important parameters to be controlled. For the coupled filtration/sorption treatment, TiO2 membranes exhibit good mechanical strength and are able to extract strontium. On the other hand in the case of strontium, composite sorbents (TiO2/foam or TiO2/tubular support) can be fully regenerated by using an acidic aqueous solution (pH = 3).