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The feasibility of applying a recently developed liquid-liquid extraction method termed Predispersed Solvent Extraction (PDSE) in an <i>ex situ</i> pump-and-treat system to remove trace amounts of dissolved chlorinated solvents like perchloroethylene (PCE) and trichloroethylene (TCE) from contaminated ground water has been investigated. In PDSE, the solvent is comminuted into globules with diameters ranging from submicron to 100 microns, and stabilized by a surfactant film prior to contact with the aqueous feed. These stabilized globules, termed oil-core aphrons (OCAs), disperse readily in water since water is the continuous phase in systems where the oil-water phase ratios can be as high as 9. Due to their fine particle size and large surface area, high extraction mass-transfer rates are achieved with minimal mixing. OCA phase separation from water can be expedited with microbubble foam flotation. Experiments in this investigation focused on PDSE process development for this groundwater remediation application. Distribution coefficients for PCE and TCE in possible OCA solvents were determined experimentally and agree with published calculated values. Various surfactant/solvent OCA formulations using the aforementioned solvents were examined with emphasis on creating a weakly stable dispersion which would maximize extraction efficiency yet destabilize sufficiently to permit rapid flotation with minimum losses in the raffinate. Accelerating phase separation, hence solvent recovery, through dispersion chemical destabilization with salts, coagulants, and flocculants at varied pH was examined with and without microbubble flotation. The presence of OCAs in the aqueous phase reduced vapor phase concentrations of PCE as much as 96% and was assessed through apparent Henry's Law constants. TCE concentrated in dodecane OCA extract was degraded with a CO-dehydrogenase enzyme complex to cis 1,2-dichloroethylene, trans 1,2-dichloroethylene, and 1,1-dichloroethylene, and vinyl chloride as a possible means of destroying TCE dissolved in the extract. Based on the implications of these experiments, the development of a PDSE <i>ex situ</i> pump-and-treat system appears technically feasible and a conceptual process layout has been provided. / Master of Science

La séparation de nanoparticules (NPs) contenues dans des milieux aqueux est un sérieux challenge pour le traitement des eaux à cause de la grande stabilité et de la nature colloïdale de ces particules. Ce travail concerne le développement de procédés efficaces de flottation pour la séparation de nanoparticules. La première partie du travail est conduite pour obtenir une connaissance plus étroite de la nature et du comportement colloïdal des nanoparticules en suspension. Des tests de modifications de leur surface et des expériences d’adsorption-agrégation sont ensuite menés pour comprendre les mécanismes d’interactions entre les NPs et des réactifs d’aide à la flottation. Deux type des techniques de flottation (la flottation à air dissout (DAF) et la flottation par des aphrons colloïdaux (CGAs)) sont utilisés : le premier type a ici pour objectif de séparer les nanoparticules par des bulles d’air avec l’aide d’acides humiques (HA), alors que le second utilise des microbulles dont la surface est fonctionnalisée par des tensioactifs (CGAs), dans l’objectif d’accroître l’efficacité de séparation. Les résultats montrent que, par mélange avec une solution basique de HA (pH 12.9), la charge de surface de nanoparticules de TiO2 (TNPs) est d’abord neutralisée par des ions OH- et ensuite écrantée par les polyanions de HA. Quand le pH des suspensions TNPs-HA est en dessous de 3 par ajout de solution mère de HA de pH 4.9-9.0, l’attraction électrostatique entre les TNPs et les anions est insuffisante, mais on observe quand même l’agrégation entre TNPs et la part colloïdale de l’HA. Par des essais de DAF en continu, le pH optimal de la solution mère de HA (pH≦ 9) et la concentration optimale en HA (11.1 mg/L COD) permettent d’éliminer plus de 95% des nanoparticules. La concentration résiduelle de HA reste à un très bas niveau même quand l’acide humique est surdosé. Quand le pH des suspensions TNPs-HA est très acide, la plupart des molécules d’acides humiques ne sont pas solubles et ne sont pas chargées. Elles peuvent s’agréger entre-elles et former un précipité colloïdal hydrophobe pour minimiser leur contact avec le milieu aqueux. En ce qui concerne les CGAs, leur caractérisation montre que la vitesse d’agitation est un paramètre crucial pour créer des aphrons de l’ordre de la dizaine de micromètres. Les CGAs peuvent être chargés négativement ou positivement en utilisant des tensioactifs adaptés. Différentes nanoparticules de SiO2 (SNPs) peuvent être efficacement (près de 100%) séparées de suspensions aqueuses par le procédé continu de flottation par CGAs. La comparaison entre flottation par CGAs et DAF montre l’avantage du premier procédé plus efficace avec une moindre quantité de surfactant / The removal of nanoparticles (NPs) from waters is a serious challenge in the water treatment field owing to the high stability and colloidal nature of particles. This study is devoted to develop effective flotation processes for NP separation. The investigation is firstly conducted to get a good knowledge of features and colloidal behaviors of NPs in suspension. Surface modification tests and adsorption-aggregation experiments are then carried out to understand the interaction mechanisms between NPs and flotation assisting reagents. Two types of flotation (dissolved air flotation (DAF) and colloidal gas aphrons (CGAs) involved flotation) were specially focused on: the former aims at using air bubbles to remove NP aggregates with the assistance of humic acid (HA), while the later employs the surface functionalized microbubbles, CGAs, to enhance the interaction of NP-bubble for the sake of high treating efficiency. Results show that, on mixing with the highly basic HA solution (pH12.9), the surface charge of TNPs is primarily neutralized by and then screened by polyanions of HA. When the pH of TNP-HA suspension is lower than 3 by adding HA stock solutions at pH4.0~9.0, the electrostatic attraction between TNPs and anions becomes insufficient but the aggregation of TNPs-colloidal HA occurs. In continuous DAF trials, the appropriate pH of HA stock solution (pH ≦ 9) and optimum HA concentration (11.1 mg/L DOC) for high TNP removals (> 95 %) are determined. The residual HA concentration remained in a low level even when HA is overdosed. When the pH of the TNP-HA suspension is highly acidic, most HA molecules are not really soluble and uncharged, and they may aggregate themselves and form hydrophobic colloidal precipitates to minimize the contact with the aqueous environment. As for the study of CGAs, the characterization results denote that introducing air flow during the CGA generation process can slow down the liquid drainage speed and may facilitate the particle separation performance; the stirring speed is a crucial parameter to create micron scale bubbles, and CGAs can be positively or negatively surface charged by using different surfactants. Different SiO2 NP (SNPs) can be efficiently separated from aqueous suspensions by the continuous CGA generation-flotation process with the highest SNP removal close to 100 %. The comparison tests between CGA-flotation and DAF denote that the former take the greater advantage because of its better treating effect and less surfactant demand