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

Cette thèse s’inscrit dans une volonté d’améliorer la compréhension des mécanismes fondamentaux de radiolyse de biomolécules par des ions accélérés, à l’échelle moléculaire. Ainsi, les ions étudiés ont été de différentes nature (H+, He2+, C6+) et de différentes énergies, correspondant à une gamme de densité de dépôt d’énergie allant de 0,3 à 1000 eV/nm.Dans le vivant, l’eau ayant une place prépondérante, la compréhension de la radiolyse de l’eau est essentielle. L’espèce la plus réactive produite en milieu aéré, le radical hydroxyle (HO•) a été quantifiée en utilisant une sonde spécifique, l’acide 3-coumarine-carboxylique.Les dégâts indirects aux biomolécules, via les espèces issues de la radiolyse de l’eau, ont été étudiés en solution aqueuse diluée sur deux systèmes : un acide aminé, la phénylalanine et une protéine, la myoglobine. Les effets directs de radiolyse ont été étudiés sur la myoglobine en gels concentrés hydratés. Les phénomènes de radiolyse ont été caractérisés pour décrire les mécanismes en jeu et les produits issus de la radiolyse de la phénylalanine ont été systématiquement identifiées et quantifiées. / The goal of this thesis is to achieve a better understanding of fundamental mechanisms of the radiolysis of biomolecules by accelerated ions, at the molecular scale. To do so, different type of ions have been used (H+, He2+, C6+) at various energies, corresponding to densities of energy deposition from 0,3 to 1000 eV/nm.The main component in biological systems is water. Therefore, the comprehension of the water radiolysis under ions irradiation is essential. One of the most reactive species produced in aerated conditions, the hydroxyl radical (HO•), has been quantified using a specific probe, the 3- carboxylic acid coumarin.Indirect effects of radiolysis on biomolecules, involving water radiolysis species, have been studied in dilute aqueous solutions on two different systems: phenylalanine, an amino acid, and a protein, myoglobin. Direct radiolysis effect were studied on concentrated hydrogels of myoglobin ad other proteins. Elucidation of radiolysis mechanisms and quantification of phenylalanine radiolysis products were systematically performed.

<p>Etanolni ekstrakti tropa odabranih sorti cvekle (Detroit, Cardeal-F1, Egipatska, Bikor i Kestrel) preči&scaron;ćeni su primenom ekstrakcije na čvrstoj fazi (SPE). Sadržaj ukupnih<br />fenolnih jedinjenja, flavonoida i betalaina u preči&scaron;ćenim ekstraktima određeni su spektrofotometrijskim metodama. HPLC analizom utvrđen je kvalitativni i kvantitativni sastav fenolnih jedinjenja i betalaina ekstrakata tropa odabranih sorti cvekle. ESR spektroskopijom ispitana je antiradikalska aktivnost ekstrakata topa cvekle na stabilne DPPH i reaktivne superoksid anjon i hidroksil radikale.<br />Spektrofotometrijski je određena antioksidativna aktivnost na DPPH radikale i redukciona sposobnost po Oyaizu u ekstraktima odabranih sorti cvekle. Ispitana je in vitro<br />antiproliferativna aktivnost frakcija ekstrakata, njihovim delovanjem na rast tri histolo&scaron;ki različite humane ćelijske linije: MCF-7 (adenokarcinom dojke), HeLa (epitelni karcinom cerviksa)i MRC-5 (fetalni fibroblastni karcinom pluća). U zavr&scaron;noj fazi rada određena je antimikrobna aktivnost ekstrakata tropa odabranih sorti cvekle.</p> / <p> Beetroot (Detroit, Cardeal-F1, Egipatska, Bikor i Kestrel)<br /> pomace ethanol extracts were purified using solid phase<br /> extraction (SPE). Contents of total phenols, flavonoids and<br /> betalains in purified extracts were determined by spectrophotometric<br /> methods. HPLC analysis were used for quantitative<br /> and qualitative characterization of phenolic compounds<br /> and betalains in investigated extracts. ESR spectroscopy<br /> was used for investigation of antiradical activity of<br /> beetroot pomace extracts on stable DPPH and reactive<br /> superoxide anion and hydroxyl radicals. Antioxidant activity<br /> was determined spectrophotometrically on DPPH radicals<br /> and reducing power according to Oyaizu in the beetroot pomace<br /> extracts. Antiproliferative activity of investigated extracts<br /> was determined in vitro, testing their influence on the<br /> growth of three histologically different human cell lines:<br /> MCF-7 (breast adenocarcinoma), HeLa (cervix epithelioid<br /> carcinoma) and MRC-5 (fetal lung). Also, antimicrobial activity<br /> of beetroot pomace extracts was determined.</p>

<p>Acetonski ekstrakti bobičastog voća iz familija Ericaceae<br />(borovnica,<em> Vaccinium myrtillus</em> L., i brusnica, <em>Vaccinium<br />macrocarpon</em> L.) i Rosaceae (&scaron;ipak, <em>Rosa canina</em> L., i glog,<br /><em>Crataegus oxyacantha</em> L.) preči&scaron;ćeni su i frakcionisani<br />primenom ekstrakcije na čvrstoj fazi (SPE). Sadržaj ukupnih<br />polifenolnih jedinjenja, flavonoida i antocijana u preči&scaron;ćenim<br />ekstraktima određeni su spektrofotometrijskim metodama.<br />HPLC analizom utvrđen je kvalitativni i kvantitativni<br />sastav frakcija ekstrakata ispitivanih bobica. ESR spektroskopijom<br />ispitana je antiradikalska aktivnost frakcija ekstrakata<br />bobica na stabilne DPPH^● i reaktivne superoksid anjon i<br />hidroksil radikale. ESR spektroskopijom ispitano je i<br />prisustvo slobodnih radikala antioksidanata nastalih tokom<br />reakcije frakcija ekstrakata bobica sa superoksid anjon<br />radikalima. U zavr&scaron;noj fazi rada ispitana je<em> in vitro</em><br />antiproliferativna aktivnost frakcija ekstrakata bobica, njihovim<br />delovanjem na rast tri histolo&scaron;ki različite humane ćelijske<br />linije: HeLa (epitelni karcinom cerviksa), HT-29 (adenokarcinom<br />debelog creva) i MCF-7 (adenokarcinom dojke).</p> / <p>Acetone extracts of berries form Ericaceae (bilberry, <em>Vaccinium<br />myrtillus</em> L., and cranberry, <em>Vaccinium macrocarpon</em><br />L.) and Rosaceae (rose hip, <em>Rosa canina</em> L., and hawthorn,<br /><em>Crataegus oxyacantha </em>L.) families were purified and fractionated<br />using solid phase extraction (SPE). Contents of total<br />polyphenols, flavonoids and anthocyanins in purified extracts<br />were determined by spectrophotometric methods.<br />HPLC analysis were used for quantitative and qualitative<br />characterization of investigated berry extracts fractions. ESR<br />spectroscopy was used for investigation of antiradical activity<br />of berry extracts fractions on stable DPPH^● and<br />reactive superoxide anion and hydroxyl radicals. The<br />presence of antioxidant free radicals formed during reaction<br />of investigated berry extracts fractions with superoxide<br />anion radicals was also investigated by ESR. Antiprolixferative<br />activity of investigated berry extracts fractions was<br />determined<em> in vitro</em>, testing their influence on the growth of<br />three histologically different human cell lines: HeLa (cervix<br />epithelioid carcinoma), HT-29 (colon adenocarcinoma) i<br />MCF-7 (breast adenocarcinoma).</p>

No description available.

No description available.

No description available.

L’objectif de ce travail consiste à étudier, d’une part, les réactions des nitrates d’alkyles avec OH qui ont un intérêt atmosphérique, et d’autre part, les réactions des radicaux OH avec les alcanes et des atomes d’oxygène avec les oléfines qui ont un intérêt pour la combustion. Toutes les réactions ont été étudiées dans des réacteurs à écoulement à basse pression, y compris le réacteur à écoulement à haute température mis en place dans le cadre de la thèse, couplés à un spectromètre de masse quadripolaire à ionisation par impact électronique. Pour les réactions OH + nitrate d’alkyle, la dépendance en température de la constante de vitesse a été mesurée pour dix nitrates d'alkyles, dont pour huit nitrates pour la première fois, sur une large plage de température. Pour six nitrates, les produits de la voie réactionnelle menant au recyclage direct de NO₂, arrachement d’atome H de carbone α, ont été observés et leur rendements mesurés. La grande quantité de données obtenues dans ce travail a été utilisée pour une mise à jour de la relation structure-activité (SAR) pour les réactions d'alkyles nitrates avec OH et a permis d'améliorer les modèles atmosphériques actuels. Les études de réactions de radicaux OH avec les trois alcanes et de l'atome O avec l’éthylène et le propène ont permis de déterminer les constantes de vitesse respectives sur une large gamme de température allant de 220 à 900 K. De plus, la distribution des produits de réactions multivoies O + oléfine en fonction de la température a été déterminée pour la première fois. Ces résultats permettront d’améliorer les modèles de combustion actuellement utilisés. / The objective of this work was to study the reactions of alkyl nitrates with OH radicals relevant to atmosphere and reactions of OH radical with alkanes and oxygen atoms with olefins of interest for combustion chemistry. All reactions were studied in low pressure flow reactors (including high temperature flow reactor developed during the thesis) coupled to a quadrupole mass spectrometer with electron impact ionization. For OH reaction with nitrates, the temperature dependence of the rate constant was measured in an extended temperature range for ten alkyl nitrates, for eight of them for the first time. For six nitrates, the products of reaction pathway leading to direct recycling of NO₂ (H atom abstraction from α carbon) were observed and their yields were measured. The large amount of data obtained in this work has been used for an update of the structure-activity relation (SAR) for the reactions of alkyl nitrates with OH and will improve existing atmospheric models. For the reactions of OH radicals with three alkanes and O atoms with ethene and propene the rate constants were measured over a wide temperature range, 220-900 K. Moreover, the distribution of the products of the multichannel reactions O + olefin was determined as a function of temperature for the first time. These results are expected to improve current combustion models.

Ce travail porte sur la stabilisation de flammes prémélangées et swirlées de mélanges combustibles méthane/hydrogène/air avec différents taux de dilution d’azote et de dioxyde de carbone. Une tige centrale permet de stabiliser des flammes pour de faibles nombres de swirl. Le sommet de la flamme interagît éventuellement avec les parois de la chambre de combustion. L’objectif ces travaux est d’améliorer la connaissance des mécanismes qui gouvernent la stabilisation et la topologie de ces flammes. Ces travaux démontrent que le nombre de swirl, la composition du mélange combustible, la géométrie de la chambre de combustion ainsi que les conditions aux limites thermiques ont une grande influence sur la forme prise par la flamme. Le dispositif expérimental permet de modifier la forme et la taille de la chambre de combustion, le diamètre du tube d’injection et le nombre de swirl. Des conditions opératoires propices aux transitions de forme de flamme sont ensuite étudiées pour différentes configurations de brûleur. Une caractérisation expérimentale fouillée d’un point de fonctionnement est réalisée grâce à la Fluorescence Induite par Laser sur le radical Hydroxyle (OH-PLIF), la Vélocimétrie par Images de Particules (PIV) et la Phosphorescence Induite par Laser de phosphores sensibles à la température (LIP). Une base de donnée de l’écoulement et des conditions aux limites associées est obtenue sans et avec combustion. Les mécanismes qui contrôlent les transitions de formes de flamme sont ensuite analysés lorsque la flamme interagit avec les parois de la chambre de combustion. L’influence de la composition du mélange combustible, de la vitesse débitante et du nombre de swirl est caractérisée et il est démontré que la transition d’une flamme en V vers une flamme en M est déclenchée par un retour de flamme dans la couche limite le long d’une des parois latérales de la chambre de combustion. Les nombres sans dimension contrôlant ces transitions sont identifiés et un modèle de prévision de la forme de ces flammes est développé. La physique déterminant les transitions de forme de flammes est différente lorsque celles-ci n’interagissent pas avec les parois de la chambre de combustion. En utilisant le signal de chimiluminescence OH* et la OH-PLIF, il est montré que la teneur en hydrogène dans le combustible a une grande influence sur la forme de flamme. L’utilisation de la LIP et de thermocouples a également permis de montrer que les conditions aux limites thermiques jouent un rôle prépondérant sur la forme de flamme. Les effets combinés de l’étirement et des pertes thermiques sont examinés par l’utilisation conjointe de la PIV et de la OH-PLIF. Il est montré que les limites d’extinction de flammes pauvres prémélangées sont réduites par les pertes thermiques et que la transition d’une flamme en M vers une flamme en V est consécutive à l’extinction du front de flamme situé dans la couche de cisaillement externe du jet soumis à un étirement trop important. Ces expériences sont complétées par une analyse de la dynamique de ces flammes. Des modulations de la vitesse débitante à basse fréquence et à haute amplitude modifient la forme de flamme. La stabilisation de flammes CH4/H2/air diluées par du N2 ou du CO2 est finalement examinée. La zone de recirculation produite par la tige centrale permet d’alimenter la base de la flamme avec des gaz brûlés chauds et de stabiliser des flammes fortement diluées. Augmenter la fraction molaire de diluant dans le combustible réduit l’intensité de lumière émise par le radical OH*. Il est également montré que la composition du diluant a un impact sur le champ de température des gaz brûlés et des surfaces de la chambre de combustion. La dilution par du CO2 augmente les pertes thermiques par rayonnement des gaz brûlés. Cela réduit l’efficacité de la chambre de combustion équipée de quatre parois transparentes. [...] / This work deals with the stabilization of premixed turbulent swirling flames of methane/hydrogen/air combustible mixtures with different dilution rates of nitrogen and carbon dioxide. A central bluff body helps stabilizing the flames at low swirl numbers. The flame tip eventually impinges the combustor peripheral wall. The general objective is to gain understanding of the mechanisms governing the stabilization and the topology of these flames. It is found that the swirl number, the combustible mixture composition, the geometry of the combustor, and the thermal boundary conditions have a strong impact on the shape taken by these flames. The experimental setup used to characterize flames topologies is first described. Flames prone to topology bifurcations are selected and are studied for different arrangement of the combustor when the combustion chamber shape and size, the injection tube diameter, and swirl number are varied. One operating condition is fully characterized under non-reactive and reactive conditions using Planar Hydroxyl Laser Induced Fluorescence (OH-PLIF), Particle Imaging Velocimetry (PIV), and Laser Induced Phosphorescence of thermographic phosphors (LIP) to generate a detailed database of the flow and the corresponding boundary conditions. An analysis is then conducted to understand the mechanisms controlling shape bifurcations when the flame interacts with the combustor peripheral wall. Effects of the combustible mixture composition, the bulk flow velocity, and the swirl number are analyzed. It is shown that the transition from a V to an M flame is triggered by a flashback of the V flame tip in the boundary layer of the combustor peripheral wall. Dimensionless numbers controlling these transitions are identified and a simplified model is developed to help the prediction of the flame shapes. The physics of these shape bifurcations differs when the flame does not interact with the combustor wall. The large influence of the hydrogen enrichment in the fuel on the flame shape is analyzed using flame chemiluminescence and OH-PLIF. LIP and thermocouple measurements demonstrate that the thermal boundary conditions still have a strong impact on the flame topology. The combined effects of strain and heat losses are investigated using joint OH-PLIF and PIV experiments. It is shown that flammability limits of premixed flames are reduced due to heat losses and the transitions from M to V shaped flames is consecutive to localized extinctions of flame front elements located in the outer shear layer of the jet flow that are submitted to large strain rates. These experiments are completed by an analysis of the dynamics of methane/hydrogen/air flames. It is shown that low frequency and high amplitude velocity modulations generated by a loudspeaker alter the shape taken by these flames. The stabilization of methane/hydrogen/air flames diluted by nitrogen and carbon dioxide is finally examined. It was possible to stabilize swirled flames featuring important dilution rates due to the presence of the bluff body, installed on the axis of the injection tube. The recirculation zone behind this element supplies hot burnt gases to the flame anchoring point. Using OH* chemiluminescence imaging, it is shown than increasing the molar fraction of diluent in the fuel reduces the light emission from excited OH* radicals. The influence of dilution on the flame chemistry is emphasized with experiments conducted at a fixed thermal power and fixed adiabatic flame temperature. It is also demonstrated that the composition of the diluent has a strong influence on the temperature field of the burnt gases and of the combustor wall surfaces. Dilution with carbon dioxide increases radiative heat losses from the burnt gases in comparison to dilution with nitrogen. This penalizes the combustor efficiency equipped with four transparent quartz walls. [...]

Les différents rejets aqueux de types industriel, artisanal et/ou hospitalier, contiennent différents contaminants organiques ou inorganiques qu’il convient d’éliminer. Selon le type de l’industrie et de l’utilisation, ces rejets auront besoin de subir un ou plusieurs traitements. Il existe de nombreuses méthodes de traitement des eaux adaptées à chaque pollution et à chaque usage. Dans le cadre de ce travail, nous nous sommes intéressés à l’utilisation d’une méthode peu onéreuse qui met en jeu les ions ferriques, ions ferreux, oxygène moléculaire et la lumière solaire (Fe(III)/Fe(II)/O2/hν) pour induire la transformation de composés organiques appartenant à deux familles de pesticides : les sulfonylurées et les organophosphorés. L’objectif majeur de l’étude consiste à la compréhension du rôle des ions de fer(II) dans le processus photocatalytique largement reporté dans la littérature ainsi que d’identifier les principaux produits formés au cours du processus. L’étude de la dégradation des sulfonylurées par excitation UV du peroxyde a démontré, sans aucune surprise, une réelle efficacité du processus. La réaction met en jeu les radicaux hydroxyles qui ont été clairement mis en évidence et quantifiés sous irradiation continue et par photolyse laser. Le processus dépend de la concentration initiale du substrat, du pH et de la concentration du photoinducteur (H2O2). La présence dans le milieu de la plupart des ions inorganiques conduit à une inhibition partielle de la dégradation. Dans le cas des ions étudiés, l’ordre de la réactivité est SO42- > Cl- > NO3- > CO32- . Cet aspect est très important à considérer lorsqu’il s’agit de traiter des eaux par le procédé UV/H2O2 . Lors de l’étude du comportement photochimique du complexe [Fe(H2O)5(OH)]2+ sous excitation à 365 nm et en simulateur solaire, la principale espèce réactive mise en jeu est le radical hydroxyle. En présence de composés organiques, une dégradation totale a pu être obtenue et ceci même pour de faibles concentrations en complexe de fer(III) (1,0x10-6 mol L-1). Il y a donc une régénération in situ et sous irradiation du fer(III). L’ensemble des expériences entreprises a permis de montrer que la régénération met en jeu non seulement le fer(II) mais également l’oxygène. La présence simultanée du fer(III) à l’état de trace et du fer(II) joue un rôle clé. En effet, l’excitation du fer(III) permet la production d’état excités qui transfèrent l’énergie aux ions de fer(II). Ces derniers états excités de fer(II) réagissent avec l’oxygène moléculaire par un processus de transfert d’électrons pour générer du fer(III) et l’anion superoxyde. La solution se trouve ainsi de plus en plus enrichie en fer(III) au fur et à mesure de l’excitation lumineuse. Sur le plan analytique, nous avons utilisé la technique LC/MS et LC/ESI/MS2 pour appréhender la structure chimique des photoproduits formés par l’étude précise des processus de fragmentation. Parmi toutes les réactions habituelles du radical hydroxyl (hydroxylation du noyau aromatique, scission du pont sulfonylurée et déméthylation), nous avons montré que certaines sulfonylurées conduisent, en milieu légèrement acide, à un processus de scission du squelette triazinique. Une telle réaction a également pu être confirmée par des études théoriques au niveau B3LYP/6-31G (d,p). La présence simultanée d’un groupement methoxy et d’une amine secondaire adjacente au cycle triazine est une condition essentielle pour une telle ouverture. L’ouverture du cycle est une étape importante pour atteindre l’objectif de l’étude qui est d’obtenir la minéralisation des solutions et ainsi le traitement des rejets aqueux de types industriel, artisanal et/ou hospitalier. / Waste waters resulting from industrial and artisanal activities as well as from hospital discharges contain numerous toxic organic and inorganic contaminants that require efficient treatment. In the present work, we employed various combinations of ferric and ferrous ions, oxygen, hydrogen peroxide and sunlight (Fe(III)/Fe(II)/O2/hν) to induce the transformation of two pesticide families: sulfonylureas and organophosphorus. The main objective of the study was devoted to the role of iron(II) species in the whole transformation process and also to the elucidation of the generated byproducts. In a first step, we used the system H2O2/ hν as a preliminary process for the degradation of the pollutant. This allowed a complete and fast removal of sulfonylureas. The reaction mainly involves hydroxyl radicals that were identified and quantified by nanosecond laser photolysis technique. The process highly depends on the initial substrate concentration, pH and the concentration of the photoinductor (H2O2). The presence of inorganic ions that could be present in waste waters was shown to inhibit the degradation, in the following decreasing order: SO42- > Cl- > NO3- > CO32- . In a second step, the study of the photochemical behavior of the iron(III) aquacomplex, [Fe(H2O)5(OH)]2+, upon light excitation at 365 nm as well as by using a solar simulator also showed the generation of hydroxyl radical together with iron(II) species. A complete elimination of studied pesticides was obtained even at low concentrations of iron(III) complex (1,0x10-6 mol L-1), indicating the high efficiency of the process. To gain insight into the degradation mechanism, the evolution of iron species upon irradiation was investigated in the absence and in the presence of molecular oxygen. The results suggested that a regeneration mechanism of iron(III) occurs through two consecutives steps. First, the excitation of iron(III) in trace concentrations, leads to the formation of iron(II) excited states through energy transfer process followed an electron transfer process that involves molecular oxygen and iron(II) excited state. As a conclusion, the solution becomes more and more enriched by iron(III) via the light excitation and in the presence of oxygen revealing the photocatalytic behavior of [Fe(H2O)5(OH)]2+. Within this work, a special attention was also devoted to the identification of products formed during the above photocatalytic process. This was performed by using liquid chromatography coupled to tandem mass spectrometry LC/ESI/MS2. The close investigation of the fragmentation processes of the generated products, permitted the establishment of precise chemical structures. In addition to the classical degradation of sulfonylureas by hydroxyl radicals (hydroxylation of the aromatic ring, the scission of sulfonylurea bridge and demethylation) a ring opening of the triazine skeleton was also obtained. This was observed under acidic conditions and was clearly confirmed by theoretical studies at the B3LYP / 6-31G (d, p) level. This triazine scission was only obtained with sulfonylures that contain a methoxy group and a secondary amine adjacent to the triazine moiety. Such ring opening constitutes an important and fundamental step when decontamination or/and mineralization of waste waters are concerned.