Surface complexation models (SCMs) have proven to be a useful tool in predicting ion adsorption at the mineral – water interface. In particular, previous research has shown that the Diffuse Layer Model (DLM), Constant Capacitance Model (CCM), and Triple Layer Model (TLM), are all capable of predicting ion adsorption in relatively simple single solute systems. To better simulate the environmental conditions experienced by groundwater sources present in the Earth’s subsurface, experimental adsorption studies have been conducted for more complex multi-solute systems. Under these conditions, SCMs have not proven to be reliable in consistently predicting ion adsorption behavior for the adsorbates of interest. This inability of these SCMs to predict ion adsorption for more complex, multi-solute systems is thought to stem from the variable site density (NS) values utilized in these models. In this research, a methodology was developed for characterizing mineral surface heterogeneity that allows for the different site density values predicted from crystallography, microscopic imaging, tritium exchange, surface saturation data, and surface charging data to all be explained using a single unified theory. This methodology was applied to a goethite mineral sample used in performing batch adsorption studies in single and bi-solute systems with Cd(II), Pb(II), and Se(IV). The adsorption behavior of these adsorbates onto the goethite sample was successfully predicted using the Charge Distribution Multi-Site Complexation (CD-MUSIC) Model and surface complexes consistent with spectroscopic data and computational molecular modeling simulations. A second, separate modeling study was performed using CD-MUSIC to predict Hg(II) adsorption onto different goethite samples of varying size and crystal morphology in single and multi-solute systems. In this study, site density values were predicted for the mineral samples studied utilizing a linear relationship observed for goethite between specific surface area and proton reactive site density. The CD-MUSIC model proved successful in predicting Hg(II) adsorption over all conditions studied while employing only surface complexes consistent with molecular scale analyses. In addition, a novel method for quantifying carbonate’s presence in experimental systems was developed. / text

Several recent studies that have proposed MUSIC models for gibbsite surfaces have purported to achieve a very good fit with potentiometric titration data. However, in order to achieve such results, several significant parameters, such as the number of surface sites, site densities, and pKa values were sometimes re-introduced in the model as fitted parameters, and physically unrealistic modeling assumptions were sometimes used. In addition, recent evidence supports the idea that some of the gibbsite potentiometric titration data from these studies may be unreliable. In order to re-interpret the potentiometric titration data, we used several recently published methods. In order to detect possible problems with estimates of gibbsite basal and edge surface area, we synthesized two gibbsite samples with different aspect ratios and characterized their surface areas using BET, AFM, and computerized image analysis routines. We also estimated pKa values for acid/base reactions at gibbsite surfaces by applying a new bond-valence method to gibbsite (001)-type and (100)-type surface structures based on ab initio calculations. The resulting pKa estimates are not to be taken as precise values due to difficulties and assumptions associated with calculating reasonable ab initio surface structures. Instead, we believe they represent a more reasonable range than has been previously estimated. Using these estimates, we propose an improved MUSIC model for gibbsite, which seems to predict surface adsorption, not perfectly, but within a reasonable range for a number of titration data sets without re-introducing any of our estimated parameters as adjustable parameters. Discrepancies that exist between model predictions and various potentiometric titration data sets are likely due to error associated with potentiometric titrations and pKa predictions.

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The adsorption behavior of silicic acid and arsenite alone and competitively on goethite over a broad pH range (3-11) at environmentally relevant concentrations was investigated utilizing pH adsorption data and zeta potential measurements. Both addition scenarios (Si before As(III) and As(III) before Si) were examined. The results of the adsorption experiments and zeta potential measurements were then used to model the single ion and competitive ion adsorption on goethite with the CD-MUSIC model implemented in the FITEQL 4.0 computer program. Silicic acid adsorption was reduced by the presence of arsenite for all but one of the adsorption scenarios examined, while in contrast silicic acid had little effect upon arsenite adsorption. However, the presence of silicic acid, regardless of the addition scenario, dramatically increased the arsenite equilibrium solution concentration over the entire pH range investigated. The CD-MUSIC model was able to predict the single ion adsorption behavior of silicic acid and arsenite on goethite. The modeled zeta potential data provided further evidence of the CD-MUSIC model's ability to describe the single anion adsorption on goethite. Our model was also able to collectively describe adsorption and zeta potential data for the low Si-arsenite adsorption scenario quite well however, our model under-predicted silicic acid adsorption for the high Si-arsenite competitive scenario. / Master of Science

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Les phénomènes d’adsorption interviennent dans les processus géochimiques gouvernant ainsi le transport des contaminants. Par ailleurs, les variations de température sont susceptibles d’influencer significativement leur comportement vis-à-vis de la surface des minéraux. Aussi, l'influence de la température sur la sorption doit être étudiée afin de mieux appréhender le devenir des éléments dans l'environnement. Dans cette optique, l'interaction entre un ion modèle, l'uranyle et deux minéraux a été étudiée. Dans un premier temps, un composé méthodologique, la monazite, a été choisi afin de déterminer la démarche à suivre pour étudier l'influence de la température sur la sorption de l'uranyle dans trois milieux plus ou moins complexants. Puis, des tests préliminaires ont été réalisés pour étudier la sorption de l'uranyle sur un composé d'intérêt industriel, la magnétite, en appliquant la démarche mise en place. Le solide a d'abord été caractérisé d'un point de vue massif puis les caractéristiques acido-basiques de sa mise en suspension dans les trois électrolytes (NaClO4, NaNO3 et Na2SO4) ont été étudiées en fonction de la température. Les constantes d'équilibre associées aux réactions de déprotonation des sites de surface ont été déterminées entre 25°C et 95°C par modélisation de courbes de titrages potentiométriques. Les simulations ont été effectuées en limitant au maximum le nombre de degrés de liberté du système. Le modèle 1-pK a donc été préféré au modèle 2-pK en raison du nombre de paramètres ajustables plus limité dans ce modèle. Des contraintes expérimentales telles que le pH de point de charge nulle ou les enthalpies déterminées par mesure directe des chaleurs associées par microcalorimétrie de mélange ont été imposées pour déterminer les constantes d'équilibre acido-basiques. La sorption de l'uranyle en fonction du pH sur le même intervalle de température a été étudiée en alliant l'acquisition de données macroscopiques telles que les sauts de sorption et la spéciation en solution à une étude structurale menée par analyse par spectrofluorimétrie laser permettant l'identification des espèces sorbées. La simulation des sauts de sorption permettant d'accéder aux constantes associées aux réactions de sorption a été réalisée en imposant les caractéristiques acido-basiques préalablement déterminées. Des mesures directes, par microcalorimétrie de mélange, des chaleurs mises en jeu lors de la sorption de l'uranyle ont permis de tester la validité de la loi de Van't Hoff sur ce phénomène. La même démarche a été suivie pour étudier l'influence de la température sur la sorption de l'uranyle sur la magnétite en milieu NaClO4 et NaNO3. Cependant, l'étude structurale par spectrofluorimétrie laser n'a pu être réalisée en raison de la couloration noire de la magnétite. / The migration of radiotoxic elements in the geosphere is mainly regulated by chemical parameters which control the partitioning of the elements between mineral phases and aqueous solutions. Variation in temperature may affect the retention properties of a mineral surface and requires a careful investigation in order to understand the radionuclides behavior in the geosphere. In this way, the interaction mechanisms between uranium(VI) and two minerals (LaPO4 and Fe3O4) have been studied. In a first step, the monazite (LaPO4) has been chosen as methodological solid in order to clearly define all the different stages needed to completely characterize the influence of temperature on the sorption phenomena. To reach that goal, three media, more or less complexants towards aqueous uranyl and the mineral surface, have been considered. Physico-chemical as well as surface acid-base properties of the solid surface have been studied by considering three electrolytes (NaClO4, NaNO3 and Na2SO4) and temperatures ranged from 25°C to 95°C. The point of zero charge has been found to be identical for perchlorate and nitrate media (pHPZC=2.1) but it was found to be one pK unit higher for the sulfate medium indicating a sorption of the background electrolyte ions. The reaction heats associated to the hydration of the solid have been measured by using microcalorimetry and the nature of the reactive surface sites has been determined by carrying out Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). On the basis of these experimental constraints, the titration curves obtained for the monazite suspensions were fitted by using the Constant Capacitance Model and the 1-pK model was preferred to characterize the surface charge evolution, due to the limited number of adjustable parameters. The surface protonation constants being determined, the behavior of U(VI) towards the monazite surface in the three electrolytes has been investigated. On the basis of both U(VI) speciation in solution and the results of a structural study carrying out by using TRLFS together with calorimetric measurements, the sorption edges have been modeled and the corresponding sorption constants determined. Since these values take into account a wide number of experimental results (both structural and thermodynamical ones) they appear to be accurate and could be extrapolated more confidently to other physico-chemical conditions. The experimental approach being validated with the methodological solid, preliminary tests have been carried out to study uranyl sorption onto a second substrate, the magnetite, more relevant than monazite in the field of radionuclides migration in the geosphere.