Soil and groundwater at many existing and former industrial areas and disposal sites is contaminated by petroleum hydrocarbons that were released into the environment. Among those petroleum hydrocarbons, fuel oil is more difficult to treat compared to gasoline and diesel fuel due to its characteristics of low volatility, low biodegradability, and low mobility. Thus, a combination of several different treatment technologies is required to remediate fuel oil contaminated soil or groundwater. The objective of this study was to assess the potential of applying Fenton-like oxidation process to remediate fuel-oil contaminated soils. The following tasks were performed in this study: (1) determination of the optimal oxidation conditions, (2) evaluation of the efficiency of chemical by Fenton-like process after the pretreatment of surfactant flushing, and (3) evaluation of the stability of H2O2 by the addition of potassium dihydrogen phosphate (KH2PO4). Total petroleum hydrocarbons (TPH) in soil were analyzed to determine the effectiveness of the oxidation treatment. Results from this study show that the highest TPH removal efficiency (84.8%) was obtained for soils containing 3%(w/w) of fuel oil when 3% of H2O2 was applied followed by 0.05% of H2O2 with 56.7% of TPH removal. Results also show that approximately 69.1% of TPH removal was detected with soils containing 5%(w/w) of fuel oil when 6% of H2O2 was applied followed by 3% of H2O2 with 56.7% of TPH removal and 0.05% of H2O2 with 32.6% of TPH removal. Results also indicate that Fenton-like process has much higher oxidation efficiency than using H2O2 alone. The oxidation efficiency was significantly affected when the contaminated soils were pretreated with surfactant. Results reveal that the maximum allowable surfactant addition was approximately 0.7% (w/w) for soils containing 0.5% (w/w) of fuel oil when 6% of H2O2 was applied. Addition of 2.2 mM of potassium dihydrogen phosphate influence could increase the stability of H2O2, but caused the decrease in the efficiency of TPH removal. During the Fenton-like reaction, pH values were close to 6 to 7. The neutral to slightly acidic conditions caused the decreased dissolution rate of iron minerals. This would also cause the decreased production of hydroxyl radicals from the surface of iron minerals. Results from the byproduct analysis show that the oxidation potential of Fenton-like process is not strong enough to completely destroy the fuel oil to non-toxic end products. The oxidation process produced byproducts containing carboxyl groups with molecular weights similar to their parent compounds.

Made available in DSpace on 2017-07-10T18:08:00Z (GMT). No. of bitstreams: 1 Thyara Campos Martins.pdf: 1837547 bytes, checksum: 733e952ccfb67393e6688fdf9fec96e7 (MD5) Previous issue date: 2013-02-14 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The objective of this study is to evaluate the performance of Fenton-like process using steel wool trade as a source of metallic iron and ferrous ions in the treatment of textile effluent. Preliminary experiments were conducted to evaluate the efficiency of the Fenton-like degradation and mineralization of organic and inorganic pollutants. The experiments were conducted in laboratory scale reactors. The operational parameters of the reactor: H2O2 molar concentration of reactants and Fe0 were optimized based on the values of total organic carbon (TOC), chemical oxygen demand (COD), turbidity and discoloration from an experimental design Delineation Central Composite Rotational (DCCR) 22 quadruplicate with the center point and another 4 axial points. Obtained good representation of the experimental data verified by analysis of variance. The efficiency of the processes used in the treatment of textile effluent was evaluated based on the parameters: decreased levels of TOC, COD, color and turbidity, as well as analysis of the behavior of the concentrations of sulfate, nitrate, hydrogen peroxide, dissolved iron, ammonia and organic nitrogen and reduced absorbance in the lengths where 320 and 600 nm. The molar ratio of the highest efficiency for conventional Fenton process was 1:0,9:27,5 to their COT:Fe2+:H2O2. Under these conditions, the process decreased by 91.06% of the TOC parameter, whereas the COD was reduced by 94.51%, 99.02% of discoloration and 99.88% of reduced turbidity. The Fenton-like process showed greater reductions of the parameters studied when subjected to 1:1,7:27,5 molar ratio of the respective TOC:Fe0:H2O2; these conditions the process showed 92.88% reduction of TOC, 93.91% reduction of COD, 98.11% of discoloration and 98.87% reducing turbidity. Both procedures showed these results to a reaction time of 720 minutes. Using the continuous flow system for the FL and FC process, the system allowed an efficient degradation of the effluent at retention times of about 720 minutes. The processes presented similar efficiencies, which demonstrates that the Fenton-like process is an effective alternative for the treatment of textile effluents. Confirming the ability of steel wool as the source of metallic iron, capable of use in oxidation processes of degradation. / O objetivo deste trabalho é avaliar o desempenho do processo Fenton-like, utilizando lã de aço comercial como fonte de ferro metálico e íons ferrosos, no tratamento de efluente têxtil. Foram realizados experimentos preliminares para avaliar a eficiência do processo Fenton-like na mineralização e degradação dos poluentes orgânicos e inorgânicos. Os experimentos foram realizados em reatores de escala laboratorial. Os parâmetros operacionais dos reatores: concentração molar dos reagentes H2O2 e Fe0, foram otimizados baseados nos valores do carbono orgânico total (COT), demanda química de oxigênio (DQO), descoloração e turbidez a partir de um planejamento experimental Delineamento Composto Central Rotacional (DCCR) 22 com quadruplicata no ponto central e mais 4 pontos axiais. Obteve-se boa representação dos dados experimentais verificada pela análise de variância. A eficiência dos processos aplicados no tratamento do efluente têxtil foi avaliada baseada pelos parâmetros: redução dos valores do COT, DQO, cor e turbidez, além da análise do comportamento das concentrações de sulfato, nitrato, peróxido de hidrogênio, ferro dissolvido, nitrogênio orgânico e amoniacal e redução da absorvância nos comprimentos de onde de 320 e 600 nm. A razão molar que apresentou maior eficiência para o processo Fenton Convencional foi de 1:0,9:27,5 respectiva ao COT:Fe2+:H2O2. Nessas condições, o processo apresentou redução de 91,06% do parâmetro COT, enquanto que a DQO apresentou redução de 94,51%, 99,02% de descoloração e 99,88% de redução da turbidez. O processo Fenton-like apresentou maiores reduções dos parâmetros estudados, quando submetido à razão molar de 1:1,7:27,5 respectivo ao COT:Fe0:H2O2; nessas condições o processo apresentou 92,88% de redução do COT, 93,91% de redução de DQO, 98,11% de descoloração e 98,87% de redução de turbidez. Ambos os processos apresentaram estes resultados para um tempo de reação de 720 minutos. Utilizando o sistema de fluxo contínuo para os processos FC e FL, o sistema permitiu uma eficiente degradação do efluente, em tempos de retenção da ordem de 720 minutos. Os processos apresentaram eficiências similares, o que demonstra que o processo Fenton-like é uma alternativa eficiente no tratamento de efluente têxtil. Atestando a capacidade da lã de aço como fonte de ferro metálico, passível de utilização em processos oxidativos de degradação.

Abstract The object of this study was to investigate the synthesis of a nanoscale zero-valent iron slurry (NZVIS) for use in Fenton-like reactions, and to evaluate its efficiency for As(III) oxidation to As(V) in spiked deionized water and simulated groundwater containing humic acid. Furthermore, this study used injection of the nanoiron slurry combined with electrokinetic processes to remediate As(III) in soil. NZVI was prepared by a chemical reduction process. The efficiency of using 3 wt% soluble starch (SS) to stabilize NZVI was also studied. It was found that the SS could keep the nanoparticles dispersed for over one day. The NZVI was characterized by XRD, FE-SEM, ESEM-EDS, and EDS-mapping, to observe its morphology and crystal structure. In this research the iron species observed took non-crystalline forms. In water batch tests, studies in deionized water were compared with those in simulated groundwater with humic acid, and dissolved oxygen content was adjusted. Injection of NZVIS oxidized As(III) to As(V) in all cases. In both deionized water and simulated groundwater, it was found that when the dissolved oxygen(DO) content was not increased, the NZVIS generated non-selective oxidant OH¡E, thus reducing the As(V) production rate. When dissolved oxygen content was increased, the DO oxidized organic matter present in the simulated groundwater, allowing the OH¡E to react further with As(III) and increasing the As(V) production rate. Finally, a test was performed in actual groundwater under optimal reaction conditions, without increasing the dissolved oxygen content, for comparison of As(V) yield. The concentration of As(V) was found to be higher in this test (As(V) Conc. = 17.55 £gg/L) than when using simulated groundwater (As(V) Conc. = 4.63 £gg/L). This study further examined NZVIS injection combined with electrokinetic (EK) technology for the remediation of soil columns containing a low concentration (initial conc. = 100 mg/kg) and a high concentration (initial conc. = 500 mg/kg) of As(III). EK alone without injection of NZVIS (Test E-1) resulted in a residual soil As(V) concentration of 24 mg/kg in the low-concentration test group. In Test E-2, where NZVIS was injected into the anode reservoir, and Test E-3, where NZVIS was injected into the cathode reservoir, residual soil As(V) concentrations were 2.3 mg/kg and 3.4 mg/kg, respectively. The high-concentration test group was comprised of Test E-4 (EK alone without injection of NZVIS), Test E-5 (NZVIS injected into anode reservoir), and Test E-6 (NZVIS injected into cathode reservoir). In these tests, only soil sections 0.2 and 0.4 (normalized distance from anode reservoir) met soil regulation standards. Residual As(V) concentrations in soil sections 0.6, 0.8, and 1.0 are much higher than the regulatory standard. In soil section 1.0, the residual As(V) concentration was less in Test E-6 than in Test E-5 (116.6 mg/kg and 183.5 mg/kg, respectively). This may be because at high pH values, the iron surface does not corrode, instead arsenic adsorption prevails. Only a fraction of negatively charged As(V) species will migrate towards the anode resulting in a relatively low soil As(V) concentration near the cathode.

Sediments are transported by the flowing water then build up on the bottom of water bodies as the materials settle. Contaminated sediments are composed of soils, sand, organic matters, and other minerals that accumulate on the bottom of water bodies and contain toxic or hazardous materials at levels that may adversely affect human health or the environment. The contaminated deposits can be decomposed and released into liquid phase by dramatic changes on environmental conditions. However, the contaminated deposits have a potential of causing changes of nature water system, especially for aquatic livings. Sediments contaminated by light non-aqueous-phase liquids (e.g., fuel oil) and heavy metal are prevalent and of a great concern. The major advantage of Fenton-like oxidation process is that the reagent components are safe to handle and environmentally benign. However, protective enclosure of contaminants with aged sediment matrices and the hydrophobic nature of contaminants limit their accessibility to treatment agents; these obstacles prevent treatment efforts from widespread successes. The interactions of hydrophobic contaminants with the soil matrix in various ways often limit contaminant availability for remediation. In order to overcome this limitation and increase contact, a novel extraction technique that utilized oxidation agent and elevated pressure in consecutive cycles of compression and decompression was developed and applied to soil slurry in the presence of chelating or oxidation agent. The objective of this study was to design a pressure-cycling system that integrates the oxidation agent. This system has the following advantages over traditional chemical treatment: (1) increased process speed, (2) lower operating costs, and (3) the transition metal elements can catalyze the oxidized pollutants. In this study, fuel oil was selected as the target compounds to evaluate the effectiveness of pressure-cycling system on the treatment of fuel oil contaminated sediment. The oxidizing agent used in this study was H2O2. The operating parameters included system pressure, pressure cycles, oxidizing agent concentration, and reaction time. Results show that approximately 38% of TPH was removed after 120 min of reaction with Fenton-like oxidation without pressurization. However, the removal efficiency increased to 47% under the pressure of 10 bar. Thus, pressure-assisted oxidation system is able to accelerate the oxidation reaction, and cause the remove the removal of TPH more effectively. To enhance TPH removal efficiency effectively and reduce the oxidant amount used, water flushing combined with pressure-assisted system as a pretreatment process was applied. Results show that TPH removal efficiency can be significantly enhanced and the amount of oxidant usage can be reduced when the pressurized water flushing was applied before the oxidation process.

Le thème principal de cette recherche est la remédiation des sols contaminés par des hydrocarbures en utilisant des traitements d'oxydation chimique à pH neutre. Les minéraux à base de fer sont susceptibles de catalyser cette réaction d'oxydation. L'étude concerne donc dans un premier temps la synthèse des minéraux réactifs contenant des espèces FeII et FeIII (la magnétite et la rouille verte) et, dans un second temps, leur utilisation pour catalyser l'oxydation chimique. Les procédés d'oxydation testés incluent l'oxydation de type « Fenton-like (FL) » et de type persulfate activé (AP). La formation de la magnétite et de la rouille verte a été étudiée par des transformations abiotiques de différents oxydes ferriques (ferrihydrite, goethite, hématite et lépidocrocite) mis en présence de cations FeII. La magnétite a été utilisée pour catalyser les oxydations (FL et AP) dans la dégradation des hydrocarbures aliphatiques et aromatiques polycycliques (HAP) à pH neutre. Une dégradation importante des hydrocarbures aliphatiques a été obtenue par ces deux oxydants, aussi bien pour des pétroles dégradés naturellement que pour un pétrole brut. L'oxydation catalysée par la magnétite a également été efficace pour la remédiation de deux sols contaminés par HAP provenant d'anciens sites de cokerie. Aucun sous-produit n'a été observé dans nos expériences d'oxydation. En revanche, une très faible dégradation des hydrocarbures a été observée lorsque les espèces FeII solubles ont été utilisées comme catalyseur. Des expériences d'oxydation ont également été réalisées en colonne. Ces études d'oxydation ont révélé l'importance du type de catalyseur utilisé pour l'oxydation, la disponibilité des HAP dans les sols et l'effet de la matrice du sol. Les résultats suggèrent que la magnétite peut être utilisée comme source de fer pour activer les deux oxydations par Fenton-like et persulfate à pH neutre. Ce travail a de fortes implications sur la remédiation par oxydation chimique in situ des sols pollués par des hydrocarbures / The main theme of this research is the use of reactive iron minerals in the remediation of hydrocarbon contaminated soils via chemical oxidation treatments at circumneutral pH. The contribution of this thesis is two-fold including the abiotic synthesis of mixed FeII-FeIII oxides considered as reactive iron minerals (magnetite and green rust) and their use to catalyze chemical oxidation. Oxidation methods tested in this study include Fenton-like (FL) and activated persulfate oxidation (AP). The formation of magnetite and green rust was studied by abiotic FeII-induced transformations of various ferric oxides like ferrihydrite, goethite, hematite and lepidocrocite. Then, the ability of magnetite was tested to catalyze chemical oxidation (FL and AP) for the degradation of aliphatic and polycyclic aromatic hydrocarbons (PAHs) at circumneutral pH. Significant degradation of oil hydrocarbons occurring in weathered as well as in crude oil was obtained by both oxidants. Magnetite catalyzed oxidation was also effective for remediation of two PAHs contaminated soils from ancient coking plant sites. No by-products were observed in all batch slurry oxidation systems. Very low hydrocarbon degradation was observed when soluble FeII was used as catalyst under the same experimental conditions. Magnetite also exhibited high reactivity to catalyze chemical oxidation in column experiments under flow through conditions. Oxidation studies revealed the importance of catalyst type for oxidation, PAHs availability in soils and the soil matrix effect. Results of this study suggest that magnetite can be used as iron source to activate both Fenton-like and persulfate oxidation at circumneutral pH. This study has important implications in the remediation of hydrocarbon polluted soils through in-situ chemical oxidation

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2017-12-20T16:30:11Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DANIELA TIDRE DE SOUZA.pdf: 1569807 bytes, checksum: a2dd69bd5899839f2401407661d74e73 (MD5) / Made available in DSpace on 2017-12-20T16:30:11Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DANIELA TIDRE DE SOUZA.pdf: 1569807 bytes, checksum: a2dd69bd5899839f2401407661d74e73 (MD5) Previous issue date: 2017-10-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A contaminação dos solos pelo derramamento de gasolina é um grande problema ambiental, principalmente devido aos hidrocarbonetos constituintes da gasolina como o benzeno, tolueno e xilenos. Desta forma, estudos de técnicas modernas de remediação de áreas contaminadas são de grande importância. Os Processos Oxidativos Avançados (POAs) são muito aplicados na remediação de áreas contaminadas com hidrocarbonetos, dentre estas, destaca-se o processo tipo-Fenton, esse processo consiste basicamente da decomposição do peróxido de hidrogênio catalisado por íons Fe3+, onde também pode ser catalisado pelas formas minerais de ferro presente no solo. Em decorrência disso, este trabalho teve como objetivo avaliar e comparar a eficiência do processo tipo-Fenton com adição de Fe3+ e utilizando o ferro mineral, assim como, avaliar o efeito da presença de etanol na gasolina durante o tratamento e a fitotoxicidade. Para as determinações utilizou-se cromatografia gasosa acoplada ao sistema de headspace, onde também houve uma extração prévia associando a adição de cloreto de sódio, vortex e ultrassom, apresentando índices de recuperação entre 79,25% a 108,41% para o benzeno. A determinação dos BTX via CG-headspace mostrou-se um método confiável uma vez que na faixa linear estudada (0,05 a 80 mg Kg-1) apresentou boa linearidade com R2=0,9989 para o benzeno e a precisão avaliada ficou entre 0,87 e 3,18%. Os resultados obtidos dos estudos de degradação mostraram que os processos foram eficientes na remoção dos BTX. Para as reações com adição de ferro (Fe3+) a redução dos BTX foi maior que 93 ± 0,08% e 91 ± 0,24% para as gasolinas com e sem etanol, respectivamente após 120 minutos de reação. E para as reações utilizando apenas o ferro mineral, a remoção foi maior que 89 ± 0,78% e 67 ± 0,49% com etanol e sem etanol. Evidenciando a eficiência dos óxidos de ferro presentes nessa amostra de solo. Apesar da elevada eficiência na remoção dos BTX, os ensaios de fitotoxicidade realizados após o tratamento com sementes de Lactuca sativa mostraram aumento na fitotoxicidade. Os resultados mostraram que após o tratamento e independente do processo utilizado não ocorreu germinação das sementes. Desta forma, os resultados indicam que subprodutos formados durante a degradação, apresentam maior toxicidade frente ao bioindicador Lactuca sativa. Desta forma, embora os processos de remediação utilizados neste estudo mostrarem ser eficientes na remoção dos BTX (remoção > 67%), o tempo do tratamento de 120 minutos não é o suficiente para remover a fitotoxicidade. / The contamination of soils by gasoline spills is a biggest environmental problem, mainly due to the hydrocarbons that derived from gasoline such as benzene, toluene and xylene. In this way, studies of modern remediation techniques of contaminated areas are important. The Advanced Oxidative Processes (AOPs) have are widely employed in remediation of areas contaminated by hydrocarbons, among the Fenton-type process, which has been used quite frequently in soil remediation. This process basically consists of the decomposition of hydrogen peroxide catalyzed by Fe3+ ions, and this process can also be catalyzed by the mineral forms of iron present in the soil. As a result, this work had as objective to evaluate and compare the efficiency of the Fenton-type process with addition of Fe3+ and using the mineral iron. As well as evaluating the effect of the presence of ethanol in gasoline during treatment and the phytotoxicity. For the determinations, gas chromatography coupled to the headspace system was used, where there was also a previous extraction associating the addition of sodium chloride, vortex and ultrasound, presenting recovery rates between 79,25% and 108,41% for benzene. The determination of BTX through CG-headspace proved to be a reliable method since in the studied linear range (0,05 to 80 mg Kg-1) showed good linearity with R2= 0.9989 for benzene and the precision evaluated was between 0,87 and 3,18%. The results obtained from the degradation studies showed that the processes were efficient in the removal of BTX. The obtained results showed that the processes were efficient in the removal of BTX. For reactions with iron addition (Fe3+) the reduction of BTX was greater than 93 ± 0,08% and 91 ± 0,24% for gasolines with and without ethanol, respectively after 120 minutes of reaction. And for reactions using only mineral iron, the removal was greater than 89 ± 0.78% and 67 ± 0.49% with ethanol and without ethanol, respectively. Evidence for the efficiency of iron oxides present in this soil sample. Despite the high efficiency of BTX removal, the phytotoxicity tests performed after treatment with Lactuca sativa seeds showed an increase in phytotoxicity. The results showed that after the treatment and regardless of the process used no germination of seeds occurred. Thus, the results indicate that by-products formed during degradation, present higher toxicity to the bioindicator Lactuca sativa. Thus, although the remediation processes used in this study prove to be efficient in removing BTX (removal> 67%), the treatment time of 120 minutes is not enough to remove phytotoxicity.

Dans ce travail de thèse, les radicaux hydroxyles et sulfates, générés par les procédés électro-Fenton et électro-persulfate utilisant une anode en fer, respectivement, ont été utilisés pour la dégradation des édulcorants synthétiques et un colorant azoïque. Les études réalisées sont essentiellement concentrées sur : efficacité de dégradation, mécanismes d'oxydation, schémas de minéralisation et évolution de la toxicité lors de traitement des polluants cibles.1. Le procédé électro-Fenton a montré une grande efficacité dans la dégradation oxydative de l'Aspartame (ASP). La dégradation et la minéralisation sont essentiellement affectées par la concentration du catalyseur (Fe2+) et l'intensité du courant. La constante de vitesse absolue de la réaction d'hydroxylation de l'ASP a été déterminée comme (5,23±0,02) x 109 M-1 s-1. Les acides oxalique, oxamique et maléique ont été identifiés comme sous-produits aliphatiques. La toxicité de la solution (méthode Microtox) augment dans un premier temps et ensuite diminue progressivement lors du traitement.(2) L'édulcorant artificiel Saccarine (SAC) a été efficacement dégradée par procédé électro-Fenton avec anodes DSA, Pt et BDD. Cependant, l'utilisation de l'anode BDD a accéléré significativement la minéralisation de la SAC. Les conditions optimales pour la minéralisation efficace de la SAC étaient: [SAC]: 0,2 mM, [Fe2+] (catalyseur): 0,2 mM, [Na2SO4] (électrolyte): 0,05 M, I (courant): 200 mA et pH: 3. Les acides oxalique, formique et maléique ont été identifiés comme sous-produits aliphatiques. La mesure de la toxicité indique une augmentation en début d'électrolyse (formation des intermédiaires toxiques) et puis une diminution progressive le long du traitement.(3) L'édulcorant artificiel Sucralose (SUC) a été complètement minéralisée en 360 min de traitement par procédé électro-Fenton avec l'anode Pt ou BDD. Le taux de minéralisation est affecté par la concentration de Fe2+ et le courant appliqué. L'efficacité du courant de minéralisation diminue avec l'augmentation du courant de 100 à 500 mA avec les deux anodes. Les acides oxalique, pyruvique, formique et glycolique ont été détectés au cours du processus de minéralisation.(4) Les solutions du colorant azoïque Orange II ont été effectivement décolorées par les radicaux sulfates générés par l'activation électrochimique du peroxydisulfate (PDS) utilisant un catalyseur solide, FeOOH (procédé CE/α-FeOOH/PDS). Le pH initial a peu d'effet sur la décoloration. La méthodologie RSM (Response Surface Methodology) basée sur le modèle Box-Behnken a été appliquée pour analyser les variables expérimentales. Les résultats indiquent que le courant a un effet positif sur la vitesse de décoloration. L'interaction du dosage de l'α-FeOOH et la concentration de PDS ont des effets significatifs. Les résultats d'analyse de variance (ANOVA) ont confirmé que les modèles proposés étaient exactes et fiables pour l'analyse des variables du procédé CE/α-FeOOH/PDS. Le catalyseur solide α-FeOOH a montré une bonne stabilité structurelle et pourrait être réutilisé.(5) Les solutions d'Orange II ont été dégradés par les radicaux sulfates obtenus par le même procédé mais avec catalyseur Fe3O4 : EC/Fe3O4/PDS. La vitesse de décoloration est affecté principalement par : pH initial de la solution, densité du courant, concentration de PDS et dosage de Fe3O4. La solution a été totalement décolorée en 60 min dans les conditions suivantes: [Orange II]0: 25 mg/L, [PDS]: 10 mM, [Fe3O4]: 0,8 g/L, densité du courant (j): 8,4 mA/cm2 et pH initial: 6,0. Les expériences de recyclage ont montré que les particules de Fe3O4 étaient stables et pourraient être réutilisées. Les spectres XPS ont montré la formation de Fe(II) sur la surface des particules de Fe3O4 lors de traitement. Les principaux intermédiaires ont été séparés et identifiés par la technique GC-MS et un schéma plausible de dégradation d'Orange II a été proposé / In this paper, electro-Fenton and sulfate radical-based electro-Fenton-like processes were used to degrade artificial sweeteners and azo dye. The results obtained during the research concern the removal efficiency, the oxidation mechanism, degradation pathway and toxicity evolution of target pollutants.(1) Electro-Fenton process was a effective method for the degradation of ASP in water. The removal and mineralization rate was affected by the Fe2+ concentration and applied current. The absolute rate constant of hydroxylation reaction of ASP was (5.23 ± 0.02) × 109 M–1 S–1. Short-chain aliphatic acids such as oxalic, oxamic and maleic acid were identified as aliphatic intermediates in the electro-Fenton process. The bacteria luminescence inhibition showed the toxicity of ASP solution decreased after it reached a maximum during the first period of the oxidation reaction.(2) Artificial sweetener SAC could be degraded effectively by electro-Fenton process with a DSA, Pt or BDD anode. However, the using of BDD anode could accelerate the mineralization of SAC. The optimal conditions for SAC removal were SAC concentration 0.2 mM, Fe2+ concentration 0.2 mM, Na2SO4 concentration 50 mM, applied current 200 mA and initial pH 3.0. Oxalic, formic, and maleic acid were observed as aliphatic byproducts of SAC during electro-Fenton process. The bacteria luminescence inhibition showed the toxicity of SAC solution increased at the beginning of electrolysis, and then it declined until the end of the reaction.(3) Artificial sweetener Sucralose could be completely mineralized in a 360 min reaction by electro-Fenton process with a Pt or BDD anode. The mineralization rate was affected by the Fe2+ concentration and applied current. The mineralization current efficiency (MCE) decreased with rising applied current from 100 to 500 mA with both Pt and BDD anode. Oxalic, pyruvic, formic and glycolic acids were detected during the oxidation of sucralose.(4) Orange II was effectively decolorized by EC/α-FeOOH/PDS process. The initial pH of Orange II solution had little effect on the decolorization of Orange II. RSM based on Box-Behnken statistical experiment design was applied to analyze the experimental variables. The response surface methodology models were derived based on the results of the pseudo-first-order decolorization rate constant and the response surface plots were developed accordingly. The results indicated the applied current showed a positive effect on the decolorization rate constant of Orange II. The interaction of α-FeOOH dosage and PDS concentration was significant. The ANOVA results confirmed that the proposed models were accurate and reiable for the analysis of the varibles of EC/α-FeOOH/PDS process. The catalystα-FeOOH showed good structural stability and could be reused.(5) Aqueous solutions of Orange II have been degraded effectively in the EC/Fe3O4/PDS process. The decolorization rate was affected by the initial pH of Orange II solution, current density, PDS concentration and Fe3O4 dosage. Orange II can be totally decolorizated in a 60 min reaction when initial Orange II concentration was 25 mg/L, PDS concentration was 10 mM, Fe3O4 dosage was 0.8 g/L, current density was 8.4 mA/cm2 and initial pH was 6.0. Recycle experiments showed Fe3O4 particles were stable and can be reused. XPS spectrum indicated Fe(II) was generated on the surface of Fe3O4 particles after reaction. The main intermediates were separated and identified by GC-MS technique and a plausible degradation pathway of Orange II was proposed

Dans ce travail de thèse, les radicaux hydroxyles et sulfates, générés par les procédés électro-Fenton et électro-persulfate utilisant une anode en fer, respectivement, ont été utilisés pour la dégradation des édulcorants synthétiques et un colorant azoïque. Les études réalisées sont essentiellement concentrées sur : efficacité de dégradation, mécanismes d'oxydation, schémas de minéralisation et évolution de la toxicité lors de traitement des polluants cibles.1. Le procédé électro-Fenton a montré une grande efficacité dans la dégradation oxydative de l'Aspartame (ASP). La dégradation et la minéralisation sont essentiellement affectées par la concentration du catalyseur (Fe2+) et l'intensité du courant. La constante de vitesse absolue de la réaction d'hydroxylation de l'ASP a été déterminée comme (5,23±0,02) x 109 M-1 s-1. Les acides oxalique, oxamique et maléique ont été identifiés comme sous-produits aliphatiques. La toxicité de la solution (méthode Microtox) augment dans un premier temps et ensuite diminue progressivement lors du traitement.(2) L'édulcorant artificiel Saccarine (SAC) a été efficacement dégradée par procédé électro-Fenton avec anodes DSA, Pt et BDD. Cependant, l'utilisation de l'anode BDD a accéléré significativement la minéralisation de la SAC. Les conditions optimales pour la minéralisation efficace de la SAC étaient: [SAC]: 0,2 mM, [Fe2+] (catalyseur): 0,2 mM, [Na2SO4] (électrolyte): 0,05 M, I (courant): 200 mA et pH: 3. Les acides oxalique, formique et maléique ont été identifiés comme sous-produits aliphatiques. La mesure de la toxicité indique une augmentation en début d'électrolyse (formation des intermédiaires toxiques) et puis une diminution progressive le long du traitement.(3) L'édulcorant artificiel Sucralose (SUC) a été complètement minéralisée en 360 min de traitement par procédé électro-Fenton avec l'anode Pt ou BDD. Le taux de minéralisation est affecté par la concentration de Fe2+ et le courant appliqué. L'efficacité du courant de minéralisation diminue avec l'augmentation du courant de 100 à 500 mA avec les deux anodes. Les acides oxalique, pyruvique, formique et glycolique ont été détectés au cours du processus de minéralisation.(4) Les solutions du colorant azoïque Orange II ont été effectivement décolorées par les radicaux sulfates générés par l'activation électrochimique du peroxydisulfate (PDS) utilisant un catalyseur solide, FeOOH (procédé CE/α-FeOOH/PDS). Le pH initial a peu d'effet sur la décoloration. La méthodologie RSM (Response Surface Methodology) basée sur le modèle Box-Behnken a été appliquée pour analyser les variables expérimentales. Les résultats indiquent que le courant a un effet positif sur la vitesse de décoloration. L'interaction du dosage de l'α-FeOOH et la concentration de PDS ont des effets significatifs. Les résultats d'analyse de variance (ANOVA) ont confirmé que les modèles proposés étaient exactes et fiables pour l'analyse des variables du procédé CE/α-FeOOH/PDS. Le catalyseur solide α-FeOOH a montré une bonne stabilité structurelle et pourrait être réutilisé.(5) Les solutions d'Orange II ont été dégradés par les radicaux sulfates obtenus par le même procédé mais avec catalyseur Fe3O4 : EC/Fe3O4/PDS. La vitesse de décoloration est affecté principalement par : pH initial de la solution, densité du courant, concentration de PDS et dosage de Fe3O4. La solution a été totalement décolorée en 60 min dans les conditions suivantes: [Orange II]0: 25 mg/L, [PDS]: 10 mM, [Fe3O4]: 0,8 g/L, densité du courant (j): 8,4 mA/cm2 et pH initial: 6,0. Les expériences de recyclage ont montré que les particules de Fe3O4 étaient stables et pourraient être réutilisées. Les spectres XPS ont montré la formation de Fe(II) sur la surface des particules de Fe3O4 lors de traitement. Les principaux intermédiaires ont été séparés et identifiés par la technique GC-MS et un schéma plausible de dégradation d'Orange II a été proposé / In this paper, electro-Fenton and sulfate radical-based electro-Fenton-like processes were used to degrade artificial sweeteners and azo dye. The results obtained during the research concern the removal efficiency, the oxidation mechanism, degradation pathway and toxicity evolution of target pollutants.(1) Electro-Fenton process was a effective method for the degradation of ASP in water. The removal and mineralization rate was affected by the Fe2+ concentration and applied current. The absolute rate constant of hydroxylation reaction of ASP was (5.23 ± 0.02) × 109 M–1 S–1. Short-chain aliphatic acids such as oxalic, oxamic and maleic acid were identified as aliphatic intermediates in the electro-Fenton process. The bacteria luminescence inhibition showed the toxicity of ASP solution decreased after it reached a maximum during the first period of the oxidation reaction.(2) Artificial sweetener SAC could be degraded effectively by electro-Fenton process with a DSA, Pt or BDD anode. However, the using of BDD anode could accelerate the mineralization of SAC. The optimal conditions for SAC removal were SAC concentration 0.2 mM, Fe2+ concentration 0.2 mM, Na2SO4 concentration 50 mM, applied current 200 mA and initial pH 3.0. Oxalic, formic, and maleic acid were observed as aliphatic byproducts of SAC during electro-Fenton process. The bacteria luminescence inhibition showed the toxicity of SAC solution increased at the beginning of electrolysis, and then it declined until the end of the reaction.(3) Artificial sweetener Sucralose could be completely mineralized in a 360 min reaction by electro-Fenton process with a Pt or BDD anode. The mineralization rate was affected by the Fe2+ concentration and applied current. The mineralization current efficiency (MCE) decreased with rising applied current from 100 to 500 mA with both Pt and BDD anode. Oxalic, pyruvic, formic and glycolic acids were detected during the oxidation of sucralose.(4) Orange II was effectively decolorized by EC/α-FeOOH/PDS process. The initial pH of Orange II solution had little effect on the decolorization of Orange II. RSM based on Box-Behnken statistical experiment design was applied to analyze the experimental variables. The response surface methodology models were derived based on the results of the pseudo-first-order decolorization rate constant and the response surface plots were developed accordingly. The results indicated the applied current showed a positive effect on the decolorization rate constant of Orange II. The interaction of α-FeOOH dosage and PDS concentration was significant. The ANOVA results confirmed that the proposed models were accurate and reiable for the analysis of the varibles of EC/α-FeOOH/PDS process. The catalystα-FeOOH showed good structural stability and could be reused.(5) Aqueous solutions of Orange II have been degraded effectively in the EC/Fe3O4/PDS process. The decolorization rate was affected by the initial pH of Orange II solution, current density, PDS concentration and Fe3O4 dosage. Orange II can be totally decolorizated in a 60 min reaction when initial Orange II concentration was 25 mg/L, PDS concentration was 10 mM, Fe3O4 dosage was 0.8 g/L, current density was 8.4 mA/cm2 and initial pH was 6.0. Recycle experiments showed Fe3O4 particles were stable and can be reused. XPS spectrum indicated Fe(II) was generated on the surface of Fe3O4 particles after reaction. The main intermediates were separated and identified by GC-MS technique and a plausible degradation pathway of Orange II was proposed

Dans cette étude, un nouveau complexe de fer est utilisé dans des processus d’oxydation avancée pour la dégradation de polluants organiques présents dans l’eau. Le fer ferrique (Fe(III)) et l’acide éthylène diamine-N,N’-disuccinique (EDDS) forment un complexe Fe(III)-EDDS dont la structure a été mise en évidence durant ce travail. Les propriétés photochimiques du complexe ont ensuite été évaluées en fonction de différents paramètres physico-chimiques dont le pH qui est apparu comme un paramètre clé pour l’efficacité des processus testés. Ensuite nous avons donc travaillé sur l’utilisation de ce complexe dans les processus de Fenton modifié, photo-Fenton et comme activateur des persulfates (S2O82-). Nos expériences ont été réalisées en présence du 4-tert-butylphénol (4-t-BP) qui est connu pour être un perturbateur endocrinien. Nous avons ensuite mis en évidence les conditions optimales du traitement pour la dégradation du 4-t-BP. Il est apparu que le pH joue un rôle très important et qu’en présence de ce complexe de fer, l’efficacité est plus importante pour des pH neutre ou légèrement basique. L’identification des radicaux oxydants responsables de la dégradation du polluant a également été réalisée. Dans ce cadre nous avons montré que le radical sulfate joue un rôle plus important que le radical hydroxyle lors du processus d’activation des persulfates. / Advanced Oxidation Processes (AOPs) have been proved to be successfully applied in the treatment of sewage. It can decolorize the wastewater, reduce the toxicity of pollutants, convert the pollutants to be a biodegradable by-product and achieve the completed mineralization of the organic pollutants. The Fenton technologies which are performed by iron-activated hydrogen peroxide (H2O2) to produce hydroxyl radical (HO•) has been widely investigated in the past few decades. Recently, Sulfate radical (SO4•-) which was produced by the activation of persulfate (S2O82-) is applied to the degradation of organic pollutants in water and soil. It is a new technology recently developed. It is also believed to be one of the most promising advanced oxidation technologies.In this study, a new iron complex is introduced to the traditional Fenton reaction. The ferric iron (Fe(III)) and Ethylene diamine-N,N′-disuccinic acid (EDDS) formed the complex named Fe(III)-EDDS. It can overcome the main disadvantage of traditional Fenton technology, which is the fact that traditional Fenton technology can only perform high efficiency in acidic condition. Simultaneously, EDDS is biodegradable and it is one of the best environment-friendly complexing agents. On the other hand, the transition metal is able to activate S2O82- to generate SO4•-. Therefore, Fe(III)-EDDS will also be applied to activate S2O82- in the present study. 4-tert-Butylphenol (4-t-BP) has been chosen as a target pollutant in this study. It is widely used as a chemical raw material and is classified as endocrine disrupting chemicals due to the estrogenic effects. The 4-t-BP degradation rate (R4-t-BP) is used to indicate the efficiency of the advanced oxidation processes which are based on Fe(III)-EDDS utilization. The main contents and conclusions of this research are shown as follows:In the first part, the chemical structure and properties of Fe(III)-EDDS and the 4-t-BP degradation efficiency in UV/Fe(III)-EDDS system were studied. The results showed that Fe(III)-EDDS was a stable complex which was formed by the Fe(III) and EDDS with the molar ratio 1:1. From the photoredox process of Fe(III)-EDDS, the formation of hydroxyl radical was confirmed including that HO• is the main species responsible for the degradation of 4-t-BP in aqueous solution. Ferrous ion (Fe(II)) was also formed during the reaction. With the increasing Fe(III)-EDDS concentration, 4-t-BP degradation rate increased but is inhibited when the Fe(III)-EDDS concentration was too high. Indeed, Fe(III)-EDDS is the scavenger of HO•. pH value had a significant effect on the degradation efficiency of 4-t-BP that was enhanced under neutral or alkaline conditions. On the one hand, Fe(III)-EDDS presented in the FeL-, Fe(OH)L2-, Fe(OH)2L3-, Fe(OH)4- four different forms under different pH conditions and they had different sensitivity to the UV light. On the other hand, pH value affected the cycle between Fe(III) and Fe(II ). The formation of hydroperoxy radicals (HO2•) and superoxide radical anions (O2•-) (pka = 4.88) as a function of pH was also one of the reasons. It was observed that O2 was an important parameter affecting the efficiency of this process. This effect of O2 is mainly due to its important role during the oxidation of the first radical formed on the pollutant. (...)

Oxidation reactions are of prime importance at an industrial level and correspond to a huge market. Oxidation reactions are widely practiced in industry and are thoroughly studied in academic and industrial laboratories. Achievements in oxidation process resulted in the development of many new selective oxidation processes. Environmental protection also relies mainly on oxidation reactions. Remarkable results obtained in this field contributed to promote the social image of chemistry which gradually changes from being the enemy of nature to becoming its friend and savior. This study dealt with two aspects regarding oxidation process. The first aspect represented an experimental study for the partial oxidation of benzene to phenol using Pd membrane in the gaseous phase. The second part was a theoretical study for some of the advanced oxidation process (AOPs) which are applied for contaminant destructions in polluted waters. Niwa and coworkers reported a one step catalytic process to convert benzene to phenol using Pd membrane. According to their work, this technique will produce a higher yield than current cumene and nitrous oxide based industrial routes to phenol. A similar system to produce phenol from benzene in one step was studied in this work. Results at low conversion of benzene to phenol were obtained with a different selectivity from the reported work. High conversion to phenol was not obtained using the same arrangement as the reported one. High conversion to phenol was obtained using a scheme different from the one reported by Niwa et al1. It was found that producing phenol from benzene is not related to Pd-membrane since phenol was produced by passing all reactants over a Pd catalyst. Within the studied experimental conditions, formation of phenol was related to Pd catalyst since Pt catalyst was not capable of activating benzene to produce phenol. Other evidence was the result of a blank experiment, where no catalyst was used. From this experiment no phenol was produced. A kinetic model for the advanced oxidation process using ultraviolet light and hydrogen peroxide (UV/H2O2) in a completely mixed batch reactor has been tested for the destruction of humic acid in aqueous solutions. Known elementary chemical reactions with the corresponding rate constants were taken from the literature and used in this model. Photochemical reaction parameters of hydrogen peroxide and humic acid were also taken from the literature. Humic acid was assumed to be mainly destroyed by direct photolysis and radicals. The rate constant for the HA- reaction was optimized from range of values in the literature. Other fitted parameters were the rate constant of direct photolysis of hydrogen peroxide and humic acid. A series of reactions were proposed for formation of organic byproducts of humic acid destruction by direct photolysis and radicals. The corresponding rate constants were optimized based on the best fit within the range of available published data. This model doesn't assume the net formation of free radicals species is zero. The model was verified by predicting the degradation of HA and H2O2 for experimental data taken from the literature. The kinetic model predicted the effect of initial HA and H2O2 concentration on the process performance regarding the residual fraction of hydrogen peroxide and nonpurgeable dissolved organic carbon (NPDOC). The kinetic model was used to study the effect of the presence of carbonate/bicarbonate on the rate of degradation of NPDOC using hydrogen peroxide and UV (H2O2/UV) oxidation. Experimental data taken from literature were used to test the kinetic model in the presence of carbonate/bicarbonate at different concentrations. The kinetic model was able to describe the trend of the experimental data. The kinetic model simulations, along with the experimental data for the conditions in this work, showed a retardation effect on the rate of degradation of NPDOC due to the presence of bicarbonate and carbonate. This effect was attributed to the scavenging of the hydroxyl radicals by carbonate and bicarbonate. A kinetic model for the degradation of methyl tert-butyl ether (MTBE) in a batch reactor applying Fenton's reagent (FeII/ H2O2) and Fenton-like reagent (Feo/ H2O2) in aqueous solutions was proposed. All of the rate and equilibrium constants for hydrogen peroxide chemistry in aqueous solutions were taken from the literature. Rate and equilibrium constants for ferric and ferrous ions reactions in this model were taken from the reported values in the literature, except for the rate constant for the reaction of ferric ions with hydrogen peroxide where it was fitted within the range that was reported in the literature. Rate constant for iron dissolution was also a fitted parameter. The mechanism of MTBE degradation by the hydroxyl radicals was proposed based on literature studies. The kinetic model was tested on available experimental data from the literature which involved the use of Fenton's reagent and Fenton-like reagent for MTBE degradation. The degradation of MTBE in Fenton's reagent work was characterized to proceed by two stages, a fast one which involved the reaction of ferrous ions with hydrogen peroxide (FeII/H2O2 stage) and another, relatively, slower stage which involved the reaction of ferric ions with hydrogen peroxide (FeIII/H2O2 stage). The experimental data of MTBE degradation in the FeII/H2O2 stage were not sufficient to validate the model, however the model predictions of MTBE degradation in the FeIII/H2O2 stage was good. Also, the model was able to predict the byproducts formation from MTBE degradation and their degradation especially methyl acetate, and tert-butyl alcohol. The effect of each proposed reaction on MTBE degradation and the byproducts formation and degradation was elucidated based on a sensitivity analysis. The kinetic model predicted the degradation of MTBE for Fenton-like reagent for the tested experimental data. Matlab (R13) was used to solve the set of ordinary nonlinear stiff differential equations that described rate of species concentrations in each advanced oxidation kinetic model. Niwa, S. et al., Science 295 (2002) 105