La sorption de CO2 et de CH4 dans des charbons a été caractérisée au laboratoire afin d'étudier la faisabilité du stockage géologique de CO2 dans les veines de charbon. La diffusion et la sorption de CO2 et de CH4 sur des charbons du bassin de Lorraine et du bassin de Gardanne ont été étudiées par une méthode gravimétrique jusqu'à une pression de 5 MPa et pour des températures variant de 283 à 333 K. La cinétique de sorption dépend du gaz utilisé, de la granulométrie, de la pression en gaz et de la température. Elle peut être représentée par un modèle unipore basé sur la loi de Fick. Le coefficient de diffusion de CO2 dans le charbon est supérieur à celui du CH4 et est d'environ 10–12 m2 s–1, valeur de diffusion assez faible. A l'équilibre, la température, la pression, le gaz utilisé, la composition des charbons et la teneur en eau sont des paramètres qui influencent la capacité de sorption sur les charbons. Le charbon du bassin de Lorraine possède une plus grande capacité de sorption de CO2 (1,6 mmol g–1, soit ~ 36 m3 t–1) que celle du charbon du bassin de Gardanne. Le modèle de Dubinin-Astakhov basé sur un remplissage volumique des pores, rend mieux compte de la sorption de CO2 et CH4 que les modèles de Dubinin-Radushkevich et de Langmuir. Par ailleurs, les mécanismes de sorption de l'eau sur le charbon ont été mis en évidence, permettant de mieux interpréter l'influence de l'eau sur la capacité de sorption des gaz. A partir de l'ensemble des résultats, une évaluation des possibilités de stockage est discutée. Il en ressort la nécessité d'études complémentaires dans le but d'améliorer la perméabilité de la veine à l'échelle du site de stockage pour permettre une meilleure injectivité du gaz / The CO2 and CH4 sorption onto coals has been characterized in laboratory in order to study the feasibility of CO2 geological storage in coal seams. The diffusion and sorption of CO2 and CH4 on coals of Lorraine and Gardanne basins have been performed from a gravimetric method until a pressure of 5 MPa and for temperatures from 283 to 333 K. The kinetics of sorption depends on the nature of gas, the grain size of coal, the gas pressure and the temperature. It can be represented by a unipore model based on Fick's law. The CO2 diffusion coefficient on coal is higher than that of CH4 and is about 10–12 m2 s–1. At equilibrium, the temperature, pressure, nature of gas, composition of coal and water content are parameters that influence the sorption capacity of coals. The coal of Lorraine basin has a greater capacity for sorption of CO2 (1.6 mmol g–1, ~ 36 m3 t–1) than that of coal of Gardanne basin. The model of Dubinin-Astakhov based on a pore volume filling, has a best fit of sorption data that Dubinin-Radushkevich and Langmuir models. Finally, the different mechanisms of water sorption on coal have been identified and can better interpret the influence of moisture on the gas sorption capacity. From all results, an assessment of capacity storage is discussed. This indicates the need for further studies in order to improve the permeability of the coal seams across the storage site for better gas injectivity

l'étude des mécanismes de sorption à l'interface passe, dans un premier temps, par la caractérisation du solide en équilibre avec le milieu pour étudier le phénomène d'hydratation de la surface du solide ; puis , dans un second temps, par l'étude du phénomène de sorption lorsque le liquide est placé à l'équilibre dans un milieu comportant les ions métalliques jouant le rôle d'adsorbat. Dans cette optique , le but du travail de thèse présenté ici est l'étude, à l'échelle moléculaire, des mécanismes de sorption associés au système UO_2^{2+}/TiO_2. Nous avons utilisé une démarche originale, consistant à étudier le système selon une approche multi-échelle.Cette approche se compose elle même de trois parties bien distinctes. En premier lieu, nous nous sommes intéressés aux données macroscopiques concernant le système d'étude. En parallèle de l'acquisition de ces données macroscopiques, nous avons employé le modèle CD-MUSIC pour le calcul des constantes d'acidité de surface du solide hydraté, qui utilise l'arrangement atomique de surface du substrat. En second lieu, nous avons effectué une étude multi-spectroscopique(SLRT, XPS, DRIFT, SHG) afin d'améliorer la compréhension du système à l'échelle moléculaire. Enfin, tous ces résultats ont été déterminés sur un même composé (TiO_2) mais sous différentes formes (phases rutile et anastase et monocristaux des phases (110), (001), et (111) pour la phase rutile). Les résultats de l'étude structurale ont permis de déterminer la coexistence de deux sites de sorption pour l'ion uranyle aquo à la surface de l'oxyde de titane et ceci quelle que soit la forme du solide étudié (poudre ou monocrystal). Il ressort de cette étude que les deux sites de sorption présentent une réactivité différente vis-à-vis de l'ion uranyle : le site le plus réactif a été attribué au site composé de deux atomes d'oxygène pontants et le site le moins réactif a été attribué au site composé par un oxygène terminal et un oxygène pontant. Désormais, nous pouvons considérer que l'étude de monocristaux permet de rendre compte des propriétés de la poudre polycristalline lors des études de sorption d'un cation sur un oxyde. Enfin , l'approche multi-échelle adoptée a permis d'obtenir une quantité importante d'informations, qui sont autant de contraintes lors de la détermination des constantes de sorption effectuée par la modélisation des données macroscopiques menée à l'aide d'un modèle de complexation de surface( modèle à capacité constante).

The main issue of this thesis was to obtain information ondiffusion and sorption behaviour on organic colloids incompacted bentonite through experimental studies. It was tostudy if bentonite is an efficient barrier for organic colloidsor not. If colloids diffuse into bentonite in sufficientconcentrations, the speciation and sorption characteristics ofdiffusing radionuclides will change. Colloids might facilitatetransport, especially of radionuclides immobilised by strongsorption on bentonite. Laboratory experiments were performed to determine thestability of humic substances (HS) and bentonite colloids insolutions of ionic strengths representative for deep graniticgroundwaters. The HS but not the bentonite colloids were foundto be stable in these conditions. The competition between complexation with HS and sorption onbentonite of the cations Sr(II) and Eu(III) were studied inbatch experiments. Eu(III) was foundto complex with HS to bigextent. If HS is present in sufficient concentrations andstable in compacted bentonite, the Eu(III)-HS will be a speciesthat has to be accounted for. Sr(II) sorption decreases in thepresence of HS at ionic strength 0.01 M, but not at 0.1 M.Sr(II) sorbs weakly on bentonite and forms weak complexes withHS. The diffusion of Sr(II) in bentonite compacted to 1.8 g/cm3dry density and equilibrated with 0.1 M NaClO4 solutions wasstudied with and without HS in the system. The HS concentrationwas varied between 0.1 and 0.2 g/l. The Sr(II) diffusion wasnot affected by the presence of HS, which is in agreement withthe competition data of complexation to HS and sorption onbentonite. Diffusion of Co(II) and Eu(III) was studied in bentonite ofcompaction 0.6-1.8 g/cm3in the presence of HS. Eu(III)diffusion without HS in the system was studied as well. Co(II)diffusivity was found to increase significantly in the presenceof HS and the Kd-values decreased drastically. The decrease inthe Kd-values was found to be ionic strength dependent. This isexplained by HS complexation capacity decreases with increasingionic strength. The results indicate that the strongly surfacecomplexed Co(II) is mobilised by HS, but the Co-HS is not theonly diffusing Co(II) species in the experimental conditions ofthis study. Considering that Eu(III) sorbs strongly on bentonite, thediffusivity of Eu(III) was found to be rather high at ionicstrength 0.01 M. The high diffusivity rates are explained bythat the cation-exchanged Eu(III) around 1 % of the totalsorption is in practise mobile. In the presence of HS, Eu(III)diffusivity increases and the sorption decrease drastically.The Eu(III)-HS seems to be the dominating Eu(III) species whenthe HS concentrations are sufficiently high, and the HSsorption and diffusivity govern the system. <b>Keywords:</b>Diffusion, sorption, complexation, stability,bentonite, humic substances, Sr(II), Co(II) and Eu(III).

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Arsenic is ubiquitous whether it is naturally occurring or produced by humans. It is found at sites on the National Priority List and at sites operated by DOE, where it is the second most commonly found contaminant. More wastes containing arsenic will be produced due to the lowering of the Maximum Contaminant Level (MCL) for arsenic in drinking water which will result in more treatment facilities for arsenic removal that will generate residuals. Furthermore, arsenic can be released from such wastes under the reduced conditions that are found in landfills. Pyrite (FeS2) is believed to be a compound that has a high affinity for arsenic and is stable under anoxic conditions. The first task of this research was to develop a method for making pyrite crystals of defined size with minimal reaction time and at high yield. Effects on the synthesis of pyrite particles of pH, the ratio of Fe/S, temperature and reaction time were investigated in batch reactor systems. Pyrite was synthesized within 24 hours at pH values ranging from pH 3.6 through pH 5.6, and at a ratio of Fe/S of 0.5. X-ray diffraction and scanning electron microscopy were used to size and characterize the pyrite particles. Experimental and analytical procedures developed for this work, included a hydride generation atomic absorption spectrometry method for measuring arsenic species (As(III), As(V)). The synthesized pyrite was applied to remove arsenic and its maximum capacity for arsenic removal was measured in batch adsorption experiments to be 3.23 μmol/g for As(III) and 113 μmol/g for As(V). Information obtained on the characteristics of chemical species before and after the reaction with arsenic showed that iron and sulfur were oxidized. Last, how strongly arsenic was bound to pyrite was investigated and it was determined that release of arsenic from As(III)-pyrite is not affected by pH, but release from As(V)-pyrite is affected by pH with minimum release in the range pH 5 to pH 8.

<p>The main issue of this thesis was to obtain information ondiffusion and sorption behaviour on organic colloids incompacted bentonite through experimental studies. It was tostudy if bentonite is an efficient barrier for organic colloidsor not. If colloids diffuse into bentonite in sufficientconcentrations, the speciation and sorption characteristics ofdiffusing radionuclides will change. Colloids might facilitatetransport, especially of radionuclides immobilised by strongsorption on bentonite.</p><p>Laboratory experiments were performed to determine thestability of humic substances (HS) and bentonite colloids insolutions of ionic strengths representative for deep graniticgroundwaters. The HS but not the bentonite colloids were foundto be stable in these conditions.</p><p>The competition between complexation with HS and sorption onbentonite of the cations Sr(II) and Eu(III) were studied inbatch experiments. Eu(III) was foundto complex with HS to bigextent. If HS is present in sufficient concentrations andstable in compacted bentonite, the Eu(III)-HS will be a speciesthat has to be accounted for. Sr(II) sorption decreases in thepresence of HS at ionic strength 0.01 M, but not at 0.1 M.Sr(II) sorbs weakly on bentonite and forms weak complexes withHS.</p><p>The diffusion of Sr(II) in bentonite compacted to 1.8 g/cm3dry density and equilibrated with 0.1 M NaClO4 solutions wasstudied with and without HS in the system. The HS concentrationwas varied between 0.1 and 0.2 g/l. The Sr(II) diffusion wasnot affected by the presence of HS, which is in agreement withthe competition data of complexation to HS and sorption onbentonite.</p><p>Diffusion of Co(II) and Eu(III) was studied in bentonite ofcompaction 0.6-1.8 g/cm3in the presence of HS. Eu(III)diffusion without HS in the system was studied as well. Co(II)diffusivity was found to increase significantly in the presenceof HS and the Kd-values decreased drastically. The decrease inthe Kd-values was found to be ionic strength dependent. This isexplained by HS complexation capacity decreases with increasingionic strength. The results indicate that the strongly surfacecomplexed Co(II) is mobilised by HS, but the Co-HS is not theonly diffusing Co(II) species in the experimental conditions ofthis study.</p><p>Considering that Eu(III) sorbs strongly on bentonite, thediffusivity of Eu(III) was found to be rather high at ionicstrength 0.01 M. The high diffusivity rates are explained bythat the cation-exchanged Eu(III) around 1 % of the totalsorption is in practise mobile. In the presence of HS, Eu(III)diffusivity increases and the sorption decrease drastically.The Eu(III)-HS seems to be the dominating Eu(III) species whenthe HS concentrations are sufficiently high, and the HSsorption and diffusivity govern the system.</p><p><b>Keywords:</b>Diffusion, sorption, complexation, stability,bentonite, humic substances, Sr(II), Co(II) and Eu(III).</p>

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Universiẗat, Diss., 2002--Heidelberg.