This study determined the potential feasibility of surface catalyzed Fenton treatment to remediate soil and groundwater contaminated with bis(2-chloroethyl ether (BCEE), bis(2-chloroethoxy) methane (BCEM), and 1,2-dichloroethane (1,2-DCA) among other contaminants. Parameters that affect the contaminant loss rate such as pH, hydrogen peroxide concentration and solid/water ratio were systematically evaluated. Batch reactors were set-up utilizing either contaminated or uncontaminated soil that was mixed with synthetic groundwater containing the contaminants of interest. The results show an increase in contaminant reduction with a decrease in pH, an increase in hydrogen peroxide concentration, or an increase in the solid/water ratio. For the same set of conditions, contaminant reduction was greater for systems utilizing contaminated soil as compared to the systems containing uncontaminated soil. In addition, specific oxygen uptake rates were measured for an activated sludge exposed to different dilutions of untreated and surface catalyzed Fenton treated water to evaluate whether the residual BCEE, BCEM, and 1,2 DCA as well as their oxidation by products were potentially inhibitory or can potentially serve as a substrate for the activated sludge. The measured specific oxygen uptake rates show that the surface catalyzed Fenton treatment enhanced the biodegradability of the contaminated groundwater and served as a substrate for the activated sludge. / Master of Science

Adequate wastewater management is a crucial element to achieve water sustainability in the petroleum refining sector, as their operations produce vast quantities of wastewater with potentially harmful contaminants. Treatment technologies are therefore pivotal for stopping these chemicals from entering the environment and protecting receiving environments. However, refining effluents are still linked to serious pollution problems, partly because little progress has been made in determining the causative agents of the observed biological effects, resulting in non-targeted treatment. Here it is shown that naphthenic acids, which have been reported as toxic and recalcitrant, are important components of refining wastewater resulting from the processing of heavy crude oil and that they have a significant contribution to the toxic effects exerted by these effluents. Furthermore, it was found that their chemical stability makes them highly resistant to remediation using Pseudomonas putida and H2O2/Fe-TAML (TetraAmido Macrocyclic Ligands) systems under laboratory conditions, and only sequential aliquots of Fe-TAML catalysts and H2O2 showed to partially degrade naphthenic acids (50 mg/L) within 72 hours. Results suggest that a combinatorial approach of Fe-TAML/H2O2 followed by biodegradation might improve current treatment options, but further optimisation is required for the biological treatment. These results can serve as a starting point for better environmental regulations relevant to oil refining wastewater resulting from heavy crude oil, as naphthenic acids are not currently considered in the effluent guidelines for the refining sector. Furthermore, the degradation of naphthenic acids under mild conditions using Fe-TAML/H2O2 systems indicates that these catalysts hold promise for the remediation of refining wastewater in real-life scenarios.

La gestion des boues de station d'épuration est un problème majeur. Dans ce travail, des charbons préparés à partir de boues de station d'épuration (SC) ont été utilisés comme support de catalyseurs. Les performances de ces catalyseurs ont été évaluées dans trois réactions d'oxydation pour le traitement de l'eau : le procédé Fenton, l'oxydation en voie humide catalytique et l'ozonation catalytique. Le catalyseur à base d'oxyde de fer supporté sur ce charbon (FeSC) est très actif dans le procédé de type Fenton pour la décoloration et la minéralisation de l'acide orange II (AOII). Les impuretés inorganiques présentes dans le charbon (cendres), telles que SiO2 et AI2O3, peuvent jouer le rôle de co-catalyseur. Le catalyseur FeSC est également très performant dans l'oxydation en voie humide catalytique du 2-chlorophénol à 120°C sous 0.9 MPa de pression partielle d'oxygène. Cependant, une lixiviation du fer est observée en cours de réaction du fait de la production de HC1 et de petits acides carboxyliques. La lixiviation du fer peut toutefois être évitée lorsque le pH du mélange réactionnel est maintenu en dessus de 4.5, sans que les performances catalytiques n'en soient affectées. Enfin, un catalyseur Mn-g-C3N4 supporté par un charbon obtenu à partir de boue de station d'épuration obtenu par modification de nitrure de carbone par des nanoparticules de manganèse a été synthétisé. L'activité catalytique de ce catalyseur composite est 1.6 fois supérieure à celle du catalyseur Mn-g-C3N4 non supporté. Ce catalyseur composite présente par ailleurs une bonne résistance à l'oxydation et une bonne stabilité, sans qu'aucune lixiviation du manganèse ne soit observée / The disposal of sewage sludge has become an issue of particular concern. In this thesis, sewage sludge derived carbon (SC) was employed as a catalyst support. The catalytic behavior of the prepared SC-based composite catalysts was investigated in three kinds of typical oxidation reactions, including heterogeneous Fenton-like oxidation, catalytic wet air oxidation (CWAO) and catalytic ozonation. Sewage sludge-derived carbon supported iron oxide catalyst (FeSC) showed high Fenton-like performances in the discoloration and mineralization of acid orange II (AOII). Inorganic components in the SC, such as SiO2 and AI2O3 may present have a co-catalytic effect upon Fenton-like reaction. FeSC catalyst also performed quite well in the CWAO of 2-CP at 120°C under 0.9 MPa oxygen partial pressure. However, iron leaching was observed due to the generation of HC1 and some small chain organic acids. Iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Finally, Mn2O3 nanoparticles modified g-C3N4 (Mn-g-C3N4) was synthetized as a novel ozonation catalyst. To enlarge the adsorption capacity of the catalyst and improve its performances in the ozonation of sulfamethoxazole, the Mn-g-C3N4 catalyst was further supported over the sewage sludge-based activated carbon (SBAC). The catalytic activity of the composite catalyst was ca. 1.6 times higher compared to the unsupported Mn-g-C3N4 catalyst. The composite catalyst also exhibited very good resistance towards oxidation, limited Mn leaching and high stability