In the past few decades, several aqueous oxidants have been employed (e.g., permanganate, persulfate) to remediate petroleum hydrocarbons. However, the majority of the research in this field has been focused primarily on the use of oxidants in treating fresh water at low groundwater temperature. In this study, bench experiments were carried out to investigate the effectiveness of persulfate (PS) as an oxidant to remediate petroleum hydrocarbons in alternative settings (saline environments at high groundwater temperature). Benzene, Toluene, Ethylbenzene, Xylenes (BTEX), Trimethylbenzenes (TMBs), and Naphthalene were the target organic compounds investigated. Three important aspects were examined during this laboratory study: 1) the evaluation of (alkaline activated and non-activated) persulfate as a chemical oxidation agent; 2) the investigation of the effect of different temperatures (10°C versus 30°C); and 3) the examination of the effect of different persulfate concentration (20 versus 100 g/L) on the reactivity of persulfate. The results showed the high potential of persulfate to remediate the target contaminants under certain conditions. In general, alkaline-activated persulfate showed a higher potential than the non-activated persulfate. However, precipitations of calcium hydroxide were observed due to the reaction between sodium hydroxide and the high concentration of calcium which will limit the use of alkaline-activated persulfate in this particular groundwater setting The results also showed that the initial concentration of persulfate and the system temperature can play important roles in enhancing the effectiveness of PS to oxidize the target contaminants. For instance, the oxidation rate of the target contaminants was seen to be dramatically increased by increasing the persulfate addition from 20 to 100 g/L as well as with increasing the system temperature from 10°C to 30°C. However, increasing both factors (temperature and concentration) accelerated the decomposition rate of PS. Lowering the system pH was tremendously successful in order to enhance the oxidation rate of all compounds. Moreover, the expected effect of the radicals scavenging at acidic pH by Cl- and Br – ,which was reported in the literatures (e.g., Pignatello et al., 2006; Grebel et al., 2010; Suri et al., 2010), was not observed in this study which might be attributed to the contribution of the produced halogen radicals to the contaminant oxidation.

In the past few decades, several aqueous oxidants have been employed (e.g., permanganate, persulfate) to remediate petroleum hydrocarbons. However, the majority of the research in this field has been focused primarily on the use of oxidants in treating fresh water at low groundwater temperature. In this study, bench experiments were carried out to investigate the effectiveness of persulfate (PS) as an oxidant to remediate petroleum hydrocarbons in alternative settings (saline environments at high groundwater temperature). Benzene, Toluene, Ethylbenzene, Xylenes (BTEX), Trimethylbenzenes (TMBs), and Naphthalene were the target organic compounds investigated. Three important aspects were examined during this laboratory study: 1) the evaluation of (alkaline activated and non-activated) persulfate as a chemical oxidation agent; 2) the investigation of the effect of different temperatures (10°C versus 30°C); and 3) the examination of the effect of different persulfate concentration (20 versus 100 g/L) on the reactivity of persulfate. The results showed the high potential of persulfate to remediate the target contaminants under certain conditions. In general, alkaline-activated persulfate showed a higher potential than the non-activated persulfate. However, precipitations of calcium hydroxide were observed due to the reaction between sodium hydroxide and the high concentration of calcium which will limit the use of alkaline-activated persulfate in this particular groundwater setting The results also showed that the initial concentration of persulfate and the system temperature can play important roles in enhancing the effectiveness of PS to oxidize the target contaminants. For instance, the oxidation rate of the target contaminants was seen to be dramatically increased by increasing the persulfate addition from 20 to 100 g/L as well as with increasing the system temperature from 10°C to 30°C. However, increasing both factors (temperature and concentration) accelerated the decomposition rate of PS. Lowering the system pH was tremendously successful in order to enhance the oxidation rate of all compounds. Moreover, the expected effect of the radicals scavenging at acidic pH by Cl- and Br – ,which was reported in the literatures (e.g., Pignatello et al., 2006; Grebel et al., 2010; Suri et al., 2010), was not observed in this study which might be attributed to the contribution of the produced halogen radicals to the contaminant oxidation.

Summary of Thesis (Chemistry)--Vanderbilt. / "Private edition, distributed by the Joint University Libraries, Nashville, Tennessee." Includes bibliographical references (p. 7).

Summary of Thesis (Chemistry)--Vanderbilt. / "Private edition, distributed by the Joint University Libraries, Nashville, Tennessee." Includes bibliographical references (p. 7).

Trichloroethylene (TCE) is one of the most common groundwater pollutants in the United States and is a suspected carcinogen. The United States Environmental Protection Agency (EPA) estimated that between 9% and 34% of the drinking water sources in the United States may contain TCE, and have set a maximum contaminant level of 5 ìg/L for drinking water. Traditional treatment technologies such as granular activated carbon and air stripping have only had marginal success at removing TCE from contaminated sites. Chemical oxidation processes have provided a promising alternative to traditional treatment methods. The objective of this research was to examine the conditions under which zero valent iron (Fe0) activates persulfate anions to produce sulfate free radicals, a powerful oxidant used for destroying organic contaminants in water. With batch experiments, it was found that persulfate activated by zero valent iron removed TCE more effectively than persulfate oxidation activated by ferrous iron. This laboratory study also investigated the influence of pH (from 2 to 10) on TCE removal. TCE was prepared in purified water and a fixed persulfate/TCE molar ratio was employed in all tests. The results indicated that this reaction occurred over a wide range of pH values. The production and destruction of daughter products cis 1,2 dichloroethylene and vinyl chloride were observed. The effect of persulfate dose on this reaction was also studied. Results showed that a molar ratio of 10/1/1 (persulfate/ZVI/TCE) yielded over 95 percent TCE destruction. Increasing the persulfate dose resulted in greater TCE destruction as well as destruction of the daughter products. Kinetic experiments at a molar ratio of 10/1/1 (persulfate/ZVI/TCE) show that approximately 90 percent of the TCE was destroyed in less than 15 minutes.

Dans ce travail, nous avons étudié la dégradation de la sulfaclozine, un antibiotique, dans des solutions aqueuses par photocatalyse (TiO2 en suspensions) ainsi que par oxydation par les ions persulfate. L'utilisation d'inhibiteurs spécifiques (KI et alcools) nous a permis de comprendre l'intervention de chacune des espèces réactives (électrons, trous, radicaux •OH) dans la dégradation de la sulfaclozine. En outre, l'identifications des produits de dégradation par LC-MS/MS et le suivi de leur cinétique d'apparition et de disparition avec et sans alcool nous a permis de proposer un mécanisme de dégradation photocatalytique faisant intervenir les trous, les radicaux •OH, les électrons, et les radicaux O2•–. Nous avons également évalués plusieurs méthodes d'activation du persulfate (UV, irradiation solaire, UV/TiO2 et Fe(II)) afin de générer des radicaux SO4•– pour dégrader la sulfaclozine. Nous avons montré qu'à pH 7, le système présentant la plus grande efficacité quelque soit la concentration de persulfate, était le système UV/TiO2/K2S2O8. L'utilisation des inhibiteurs spécifiques des radicaux •OH et SO4•– a permis de constater que le pH a un effet important sur le rôle de chacun de ces radicaux dans la dégradation de la sulfaclozine. Les constantes de vitesse de la réaction de la sulfaclozine avec les radicaux •OH et SO4•– ont été déterminées et des valeurs proches ont été trouvées (?109 M-1s-1). Nous avons également étudié l'effet des principaux ions constituants de l'eau sur la dégradation de la sulfaclozine dans les trois systèmes suivants: UV/TiO2, UV/TiO2/K2S2O8 et UV/K2S2O8. Cette étude a montré que les bicarbonates et les phosphates accélèrent la dégradation photocatalytique alors qu'aucun effet n'a été observé dans le système UV/K2S2O8. En ce qui concerne les ions chlorures et nitrates nous avons montré qu'ils augmentaient l'adsorption de la sulfaclozine à la surface de TiO2 mais n'accéléraient pas significativement la réaction de dégradation / In this work, we studied the degradation of the antibiotic sulfaclozine in aqueous solutions by photocatalysis (on TiO2 suspensions) as well as by persulfate ions. The use of specific inhibitors (KI and alcohols) allowed us to understand the intervention of each of the reactive species (electrons, holes, radicals •OH) in the degradation of sulfaclozine. In addition, the identification of the by-products by LC-MS / MS and the monitoring of their appearance and disappearance kinetics, allowed us to propose a photocatalytic degradation mechanism involving TiO2 holes, •OH radicals, electrons, and O2•– radicals. We also evaluated several methods for persulfate activation (UV, sunlight, UV / TiO2 and Fe (II)) to generate SO4•–. We have shown that at pH 7, the system having the highest efficiency, regardless of persulfate concentration, was the UV/TiO2/K2S2O8 system. The use of specific inhibitors of •OH and SO4•– radicals showed that pH has a significant effect on the role of each of these radicals in the sulfaclozine degradation. Moreover, the reaction rate constants of sulfaclozine with •OH radicals and with SO4•– radicals were determined and close values were found (?109 M-1s-1). We also studied the effect of the main water constituents on the degradation of sulfaclozine in the following three systems: UV/TiO2, UV/TiO2/K2S2O8 and UV/K2S2O8. This study showed that bicarbonate and phosphate accelerated the photocatalytic degradation of sulfaclozine while no effect was observed in the UV/K2S2O8 system. Regarding chloride and nitrate ions, we obtained an enhancement in sulfaclozine adsorption on the surface of TiO2 but no significant enhancement of the degradation rate was observed

Due to the toxicity and prevalence of BTEX contaminants (benzene, toluene, ethylbenzene, and xylenes) at hazardous waste sites, approaches for their remediation are of interest, especially those that particularly address benzene, which is often the limiting factor for achieving regulatory cleanup at these contaminated sites. In situ chemical oxidation (ISCO) is a viable technology for BTEX destruction, and hydrogen peroxide and sodium persulfate are two oxidants of interest for BTEX treatment.Laboratory studies were conducted to compare BTEX contaminant destruction and oxidant persistence for these two oxidants and for varied methods of oxidant activation/propagation. Additionally, studies were performed to compare contaminant destruction and oxidant persistence in laboratory contaminant spike systems vs. field site contaminant systems. Finally, contaminant destruction and oxidant persistence in field porous media with varied characteristics were evaluated. Contaminant and oxidant concentrations were measured at multiple time points over a three-week reaction period in each oxidant and oxidant activation/propagation system.Under the comparable conditions evaluated here, sodium persulfate systems demonstrated greater BTEX contaminant destruction and greater oxidant persistence than hydrogen peroxide systems. FeSO4 and citric acid activation of sodium persulfate resulted in greater BTEX destruction and greater oxidant persistence than pH adjustment or hydrogen peroxide activation in both laboratory contaminant spike systems and field gas condensate systems. Additionally, results indicate that the response of the contaminant(s) and oxidant (extent and rate of depletion) are both contaminant-and porous media type-dependent.

Ce travail de thèse a porté sur l'élimination d'un pesticide, l'imazalil, en phase aqueuse par trois procédés de dégradation (UV/TiO2, UV/TiO2/K2S2O8 et UV/K2S2O8) en mettant en oeuvre les outils analytiques nécessaires pour identifier les photoproduits de dégradation, suivre leur cinétique de formation et la minéralisation. L'ajout de K2S2O8 est bénéfique pour la dégradation et la minéralisation car il produit des radicaux sulfates qui sont des espèces oxydantes puissantes. Par ailleurs, le rôle des espèces radicalaires a été mis en évidence dans les trois systèmes de dégradation par des inhibiteurs de radicaux tels que les alcools (inhibiteurs des radicaux OH•). Dans une première partie, la dégradation de l'imazalil a été réalisée dans le système UV/TiO2 et les principaux photoproduits ont été identifiés par LC/MS/MS, leurs cinétiques ont été tracées. La minéralisation a été suivie et un mécanisme de dégradation a été proposé. La dégradation se déroule selon deux voies, par l'attaque des radicaux OH• ou par les trous. Dans une deuxième partie, la méthodologie de plans d'expériences a été établie dans le système UV/TiO2/K2S2O8 afin i) d'identifier les paramètres les plus influents et leurs interactions et ii) de déterminer les conditions expérimentales les plus favorables à la dégradation. Enfin, la dégradation de l'imazalil a été comparée dans les trois systèmes de dégradation en utilisant différentes concentrations de persulfate et différents pH. Il est apparu que la dégradation dans UV/TiO2, est plus efficace en milieu basique alors le pH acide est plus favorable à la dégradation de l'imazalil dans le système UV/TiO2/K2S2O8. Par contre, le pH ne joue pas un rôle important dans le système UV/K2S2O8 / The aim of this thesis was the degradation of the pesticide imazalil in water in three different systems of degradation (UV/TiO2, UV/TiO2/K2S2O8 and UV/K2S2O8). Analytical techniques were used to identify photoproducts, to follow their kinetics and mineralization. The addition of K2S2O8 is beneficial for the degradation and mineralization because it produces sulfate radicals that are powerful oxidizing species. In addition, the role of radical species has been highlighted in the three systems of degradation by using scavengers of these radicals such as alcohols (hydroxyl radical scavenger). In the first part, the degradation of imazalil was performed in the system UV/TiO2 and the main photoproducts were identified by LC/MS/MS also their kinetics were plotted. Furthermore, mineralization was followed and degradation mechanism was proposed. The degradation of imazalil could happen in two ways, by the attack of OH• radicals or by holes. In the second part, the methodology of experimental design was established in the system UV/TiO2/K2S2O8 to identify the most influential parameters also their interactions and to determine the experimental conditions that are most favorable to the degradation. Finally, the degradation of imazalil was compared in the three degradation systems using different concentrations of persulfate and different pH. It appears that the degradation in UV/TiO2 is more efficient in alkaline medium while the acidic pH is more favorable to the degradation of imazalil in the system UV/TiO2/K2S2O8. On the other hand, the pH does not play an important role in the system UV/K2S2O8

Polyfluorinated compounds (PFCs) are a class of anthropogenic chemicals that have been found in groundwater and wastewater around the world. Perfluoroctane sulfonate (PFOS) and perfluoroctanoic acid (PFOA) are primarily used for industrial surfactants, and aqueous film forming foams (AFFFs). These PFCs and many of their constituents have been found to be carcinogenic to humans and other animals. A simple method for defluorination of these compounds is needed. Advanced oxidation of PFOS, PFHxS, and PFBS-k was carried out using activated sodium persulfate through ultrasonic irradiation with the following condition; [PFC] = 20 millimolar (mM), [Na2S2O8] = 25 mM, pH = 7, and 25°C. Fluoride concentrations were quantified by ion chromatography (IC). In laboratory experiments, batch reactions of PFBS solutions were conducted in purified water at different pH conditions and N2S¬2O8: PFBS molar ratios of 1:1, 2:1, 10:1, and 100:1 respectively. Solution pH was maintained at 7 using HNO3. Of the three compounds, PFHxS had the greatest defluorination (11%) after 120 minutes reaction time. However, PFBS-K had the greatest increase in defluorination (115%) between the control ultrasound (US) experiment and the combination experiment. When Na2S2O8 was increased, the defluorination ratio of PFBS decreased. This decrease was partly attributed to scavenging reactions between SO4¯• and S2O8²¯. These results show a synergism between ultrasonic irradiation and activated sodium persulfate as a form of advanced oxidation. Recommendations for further research into defluorination of PFOS and its constituents by ultrasonic degradation include: the use of high performance liquid chromatograph with accompanying mass spectrometry (HPLC/MS), the use of an ultrasonic probe with alternate frequencies, and the effects of surface tension on defluorination.

Abstract This work investigates the kinetics of the emulsion polymerization of vinyl acetate. Several aspects of this system have been clarified, including the induced decomposition of persulfate, retardation by oxygen and entry by, and analysis of, the aqueous phase oligomeric radicals. It has been shown that the retardation period observed in the emulsion polymerization of VAc can be explained by the effect of traces of oxygen (< 10-6 M) on the entry efficiency of the initiator-derived aqueous-phase oligomeric radicals. Comparison of rates of polymerization in V and persulfate -initiated polymerizations together with electrospray mass spectrometry of aqueous phase oligomers, has shown that the mechanism for the induced decomposition of persulfate by vinyl acetate is chain transfer to initiator from aqueous-phase oligomeric radicals. A value has been determined for the rate coefficient for transfer to initiator, by fitting literature data to a model based on this mechanism. The reported independence of the rate of polymerization from the monomer concentration in the emulsion polymerization of vinyl acetate has been investigated. Possible explanations for this behaviour have been proposed and tested in this work, by measuring radical-loss rates directly with y-relaxation techniques. Although the Y relaxations were found to be affected by experimental artefacts, it has been demonstrated that rapid exit is not responsible for the high radical-loss rates in this system. The major artefact identified in the y relaxations was the significant effect of relatively small exotherms on relaxation behaviour, Methodologies were developed for correcting affected data and for avoiding exotherms under certain conditions. Arrhenius parameters were determined for the rate coefficient for chain transfer to monomer using the In^M method, which utilises the whole MWD. This section of the work is incomplete, for reasons detailed in chapter 5. However, as a preliminary indication it was found that the frequency factor was 106.38 M-1 s-1 and the activation energy was 38.8 kJ mol-1.