Les hydrogénases [FeFe] sont des métalloenzymes capables de catalyser de façon réversible la production et l’oxydation du dihydrogène. Depuis que la structure du site actif des hydrogénases [FeFe] a été déterminée, de nombreux modèles bio-inspirés ont été élaborés et étudiés en vue de comprendre et de reproduire le fonctionnement de cette classe d’enzyme. Le site actif des hydrogénases [FeFe], le cluster-H, présente un état entatique caractérisé par une conformation particulière permettant d’activer efficacement la conversion H+/H2. Dans la littérature, très peu de modèles reproduisant une telle conformation dans l’état réduit Hred (FeIFeI) du site actif ont été décrits. Notre équipe a obtenu récemment un complexe FeIFeI de formule [Fe2(CO)4(ҡ 2-dmpe)(μ-adtBn)] (adtBn= {SCH2}2NCH2C6H5, dmpe = (CH3)2PCH2-CH2P(CH3)2), présentant une conformation ‘inversée’, à l’état solide, permettant de mimer la géométrie particulière du cluster-H. Cette conformation est stabilisée dans ce dérivé par la présence d’un pont dithiolate encombré, d’une liaison agostique et par la coordination dissymétrique d'un ligand bidentate bon σ-donneur. Les travaux de cette thèse ont été consacrés à l’étude du comportement électrochimique en oxydation de ce composé, [Fe2(CO)4(ҡ2-dmpe)(μ-adtBn)], dans différents solvants et en présence de substrats, comme CO, RNC et P(OMe)3, en vue de comprendre les mécanismes impliqués dans ces processus redox. Les oxydations chimiques du complexe [Fe2(CO)4(ҡ2-dmpe)(μ-adtBn)] ont permis de compléter l’identification des espèces formées qui ont été caractérisées par différentes méthodes spectroscopiques (IR, RMN) et par diffraction des rayons X. / [FeFe]-Hydrogenases are metalloenzymes having the capacity to catalyze efficiently both the production of H2 and its oxidation. Since the structure of the active site of [FeFe]-Hydrogenases has been determined, many bio-inspired models have been synthesized and studied to understand and to mimick the functioning of this class of enzyme. The active site of the [FeFe]-hydrogenases, the Hcluster, presents an entatic state characterized by a particular conformation that allows an efficient H+/H2 conversion. Very few models mimicking such a conformation in the reduced state, Hred (FeIFeI), of the active site have been described in the literature. Our group recently obtained a FeIFeI complex [Fe2(CO)4(k2-dmpe)(μ-adtBn)] (adtBn = {SCH2}2NCH2C6H5, dmpe = (CH3)2PCH2-CH2P(CH3)2), having an 'inverted' conformation, in the solid state, that mimicks the particular geometry of the H-cluster. This conformation is stabilized in this derivative by the presence of a crowded dithiolate bridge, an agostic interaction and the dissymmetrical coordination of a chelating good σ-donor ligand. The works in this thesis have been devoted to the study of the electrochemical properties in oxidation of the complex [Fe2(CO)4(k2-dmpe)(μ-adtBn)] in various solvents and in the presence of substrates, such as CO, RNC, P(OMe)3, in order to understand the mechanisms involved in these redox processes. The chemical oxidations of the complex [Fe2(CO)4(k2-dmpe)(μ-adtBn)] have been also performed in order to identify the species formed by oxidation. They were characterized using various spectroscopic methods (IR, NMR) and X-ray diffraction.

Der seit vielen Jahren etablierte Summenparameter DOC (dissolved organic carbon - gelöster organischer Kohlenstoff) wird u. a. standardmäßig für die Überwachung der Wasserqualität und zur Bewertung der Effizienz von Verfahren der Wasserbehandlung eingesetzt. Für eine möglichst kurze Reaktionszeit, z. B. im Fall von Havarien oder anderen Ereignissen, sind zeitlich hoch aufgelöste und verlässliche DOC-Daten von großer Bedeutung. Die konventionellen DOC-Bestimmungsmethoden basieren in der Regel nach einer Probenahme auf Konservierung, Transport und anschließender Analyse der Probe in einem stationären Labor. Bei einer schlechten Laborinfrastruktur birgt dieser Ansatz das Risiko, durch längere Lagerung bzw. Transport der Proben falsche und verspätete Ergebnisse zu liefern. Das Ziel der vorliegenden Arbeit be-stand darin, einen tragbaren und dennoch zuverlässigen Analysator für die DOC-Analyse vor Ort zu entwickeln. Basis dieses Messgerätes bildet eine ungeteilte, gal-vanostatisch betriebene Elektrolysezelle mit bordotierter Diamantelektrode. Die anodische Generierung von •OH- und SO4•--Radikalen als Oxidationsmittel, die In- situ-Bildung des Trägergases und die Kinetik des DOC-Abbaus wurden systematisch untersucht. Zudem wurde der Einfluss wichtiger verfahrenstechnischer und hydro-chemischer Parameter betrachtet und für eine Anwendung in der Umweltanalytik optimiert. Abgeschlossen wurde die Entwicklung mit der technischen Optimierung eines tragbaren Prototyps. Dieser wurde validiert und mit etablierten Verfahren ver-glichen sowie erfolgreich im Rahmen eines aktuellen Monitoringprogramms in Nordindien eingesetzt. Die wichtigsten Merkmale des tragbaren DOC-Analysators sind die kompakte Bauweise sowie der Verzicht auf hochreine Gase, Katalysatoren oder eine Verbrennungstechnologie. Zudem weist die Bestimmungsmethode eine hohe Robustheit in Bezug auf Art und Konzentration der Analyten sowie der Matrix auf und ermöglicht eine kurze Analysezeit sowie eine zuverlässige Bestimmung des DOC vor Ort. / Dissolved organic carbon (DOC) is an indispensable analytical parameter for water quality control. This applies to both monitoring of aquatic ecosystems and evaluation of the efficiency of drinking and waste water treatment processes. The conventional DOC determination methods consist of on-site sampling and subsequent analysis in a stationary laboratory. Storage and transport of samples may lead to significant un-certainties in measurement results and delayed findings. For this reason, the availability of suitable on-site analysis techniques is particularly important in coun-tries with an insufficient laboratory infrastructure. Therefore, the objective of the present study was to develop a portable and reliable analyzer for on-site DOC analy-sis. The core element of this analyzer is an undivided electrolysis cell equipped with a boron doped diamond electrode for an in-situ generation of •OH and SO4•- radicals as oxidizing agents. The influence of process and hydrochemical parameters on the generation of in-situ oxidizing agents, in-situ carrier gas and the DOC decomposition kinetic were systematically investigated and optimized for environmental analyses. Finally, a technical optimization of the portable prototype was conducted. The result-ing prototype was validated and successfully compared with established methods. Subsequently, the developed prototype was used in an ongoing monitoring program in northern India. The key features of the portable DOC analyzer are the independ-ence from high-purity gases, catalysts or combustion technology. In addition, this determination method shows a high robustness in terms of type and concentration of analytes and matrices. The short analysis time as well as a reliable determination of the DOC on site prove the practicality of the new technical approach.

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Free radical driven lipid peroxidation is a chain reaction which can lead to oxidative degradation of biological membranes. Propagation vs. termination rates of peroxidation in biological membranes are determined by a variety of factors including fatty acyl chain composition, presence of antioxidants, as well as biophysical properties of mono- or bilayers. Sphingomyelins (SMs), a class of sphingophospholipids, were previously described to inhibit lipid oxidation most probably via the formation of H-bond network within membranes. To address the “antioxidant” potential of SMs, we performed LC-MS/MS analysis of model SM/glycerophosphatidylcholine (PC) liposomes with different SM fraction after induction of radical driven lipid peroxidation. Increasing SM fraction led to a strong suppression of lipid peroxidation. Electrochemical oxidation of non-liposomal SMs eliminated the observed effect, indicating the importance of membrane structure for inhibition of peroxidation propagation. High resolution MS analysis of lipid peroxidation products (LPPs) observed in in vitro oxidized SM/PC liposomes allowed to identify and relatively quantify SM- and PC-derived LPPs. Moreover, mapping quantified LPPs to the known pathways of lipid peroxidation allowed to demonstrate significant decrease in mono-hydroxy(epoxy) LPPs relative to mono-keto derivatives in SM-rich liposomes. The results presented here illustrate an important property of SMs in biological membranes, acting as “biophysical antioxidant”. Furthermore, a ratio between mono-keto/mono-hydroxy(epoxy) oxidized species can be used as a marker of lipid peroxidation propagation in the presence of different antioxidants.

Landfilling is the most common approach to dispose of municipal solid wastes but inevitably leads to leachate formation. Persistent UV quenching substances (UVQS) in landfill leachate can affect the effectiveness of UV disinfection in municipal wastewater treatment systems when leachate co-treatment is applied. Membrane electrochemical reactor (MER) treatment was investigated to reduce the UV quenching capability and simultaneously recover resources in the leachate as an effective onsite pre-treatment. Ion-selective membranes were used in this MER to create two different conditions: a low-pH anolyte for organic oxidation and a high-pH catholyte for ammonia recovery. The MER achieved significantly higher removals of both dissolved organic carbon and UV254nm absorbance than membrane-less electrochemical treatment. The MER was able to remove a large percentage of total nitrogen from the leachate while recovering about half of the influent ammonia in the catholyte with less specific energy consumption. The second study coupled MER with Fenton oxidation through providing synergistic benefits with the low solution pH, reduced organics, and ammonia removal. This two-stage coupled system reduced the more leachate COD than the standalone Fenton process treating raw leachate. Also, the usage of chemicals as Fenton reagents has been greatly reduced: FeSO4 and H2O2 by 39%, H2SO4 by 100%, and NaOH by 55%. Consequently, the sludge production was reduced by 51% in weight and 12% in volume. Despite electricity consumption by the MER, the coupled system cost $4.76 per m3 leachate less than the standalone Fenton treatment. More notably, direct Fenton oxidation removed only 21% of ammonia; in comparison, the MER-Fenton system removed ammonia by 98% with the possibility for recovery at a rate of 30.6 -55.2 kg N m-3 reactor d-1. Those results demonstrated that coupling MER with the Fenton process could mitigate some inherent drawbacks of Fenton oxidation such as ineffective ammonia removal, high acid and chemical reagents dose requirements, and a large amount of sludge generation. The third study investigated the formation of total halogenated organics (DBP) and the associated toxicity as the side effect of leachate treatment in the MER. Compared to the 4538±100 µg L-1 from the control membrane-less electrochemical oxidation reactor, the amount of DBP generated in the MER only accounted for 19.1±4.5 % after the same treatment period. The total toxicity value (26.6 ×10-3 ) was low for MER effluent, only 15.1% of that in the control group. Both high pH and high ammonia concentration introduced more DBP mass and toxicity production after MER treatment. DBP concentrations were shown to increase with applied current density and possible temperature raise. With 67.5% of DBP mass concentration and 74.4% of the additive toxicity removal, the granular activated carbon (GAC) electrode system was shown more effective than GAC adsorption alone in remediating DBP harmful effects. This dissertation introduced MER as a promising technology for the treatment of leachate through performance demonstration, process integration and by-product remediation. / Doctor of Philosophy / Municipal solid waste is often disposed of in landfills because of the most economics and convenience. However, one of the most challenging problems is the leachate formation and treatment. In the US, leachate is currently often diluted in domestic wastewater treatment systems; meanwhile, the persistent contaminants in landfill leachate can lower the effectiveness of UV disinfection and result in high cost and permit violation. In this study, the membrane electrochemical reactor (MER) using electricity as the driving force was applied to solve the issue and simultaneously recover valuable resources in the leachate. Membranes as a barrier for selective ions were used in this MER to create two different conditions with different purposes: a low-pH anolyte for organic oxidation and a high-pH catholyte for ammonia recovery. The MER achieved significantly higher contaminants removals than membrane-less electrochemical treatment. The second study coupled MER with one of the established advanced oxidation processes, also known as Fenton oxidation through providing mutual benefits with the low solution pH, reduced organics, and ammonia removal/recovery. This two-stage coupled system reduced the leachate contaminants effectively towards the direct discharge standard. In addition, the usage of chemical reagents, as well as the amount of process residual, has significantly been reduced. The third study investigated the formation of by-products as the side effect of leachate treatment in the MER. Compared to the membrane-less reactor, the undesirable by-products generated in the MER only accounted for one fifth after the same treatment period. A granular activated carbon electrode system was shown effective in remediating the harmful effects. This dissertation introduced MER as a promising technology for the treatment of leachate as one of the toughest wastewaters.

O lixiviado de aterro sanitário é um efluente gerado a partir da mistura de líquidos produzidos na degradação de resíduos sólidos e a água pluvial que infiltra o depósito de material. Estudos na literatura, abordando tratamento de lixiviados de aterro sanitário, indicam que os processos biológicos podem não ser suficientes para que os padrões de lançamento vigentes na legislação sejam cumpridos. Neste contexto os processos oxidativos avançados estão sendo apontados como uma alternativa atrativa para efluentes que apresentam baixa biodegradabilidade. A presente pesquisa objetivou avaliar, em escala de bancada, a tratabilidade do lixiviado de aterro sanitário com aplicação do tratamento de oxidação eletroquímica seguida pelo tratamento biológico de um sistema de lodos ativados operado em batelada. A eletro-oxidação promove a remoção ou degradação de espécies poluentes, direta ou indiretamente, por meio de processos que não necessitam de adição de grandes quantidades de produtos químicos. Nos ensaios realizados com lixiviado bruto e com lixiviado alcalinizado submetido ao tratamento físico-químico de air stripping não houve necessidade de adicionar eletrólitos suporte para a oxidação química ocorrer e ao longo de tais ensaios a matéria foi mensurada quanto à DQO, COT e COD. Quando aplicada a eletro-oxidação no lixiviado bruto (sem tratamento prévio), houve 87% de remoção de DQO utilizando o anodo DDB com aplicação de 48 A h L-1 (densidade de corrente de 100 mA cm-2) e 65% de remoção da DQO quando utilizado o anodo DSA, nas mesmas condições. Analogamente, foram obtidos valores percentuais de remoção de COT de 70 e 60%, respectivamente e ainda 61 e 67% em relação ao COD. A fim de se complementar os estudos quanto à atuação da eletroquímica no tratamento do lixiviado de aterros sanitários, o efluente eletro-oxidado foi adicionado a um sistema de lodos ativados em duas proporções volumétricas distintas (2,5 e 5%) combinadas com esgoto sanitário (97,5 e 95%, respectivamente). Para controle e possível análise na eficiência, foram realizados ensaios com lixiviado bruto (5% de lixiviado bruto e 95% de esgoto sanitário) e somente esgoto sanitário (100%). Foram obtidos valores de remoção de DQO de: 75% em condição 100% esgoto sanitário, 64% com adição 2,5% de lixiviado eletro-oxidado, 57% com adição de 5% de lixiviado eletro-oxidado e 38% com adição de 5% de lixiviado bruto, além de valores percentuais de remoção de COT em cerca de 56, 52, 47 e 37%, respectivamente. E ainda foram obtida remoções nos valores de DBO na ordem de 91, 87, 64 e 24%, respectivamente. De forma geral, o sistema combinado proposto atingiu eficiências consideráveis e se mostrou compatível com o intuito de se estudar o aumento da tratabilidade por meio da aplicação de processos eletroquímicos em lixiviado bruto. / The landfill leachate is a wastewater generated from the mixture of liquids produced in the degradation of solid waste and rainwater that infiltrates the landfill. Studies in the literature approaching the treatment of landfill leachate indicate that biological processes may not be sufficient for the discharge standards prevailing in the present legislation. In this context the advanced oxidation processes (AOP) are being singled out as an attractive alternative for wastewater with a low biodegradability. This study aimed to evaluate, in a bench scale treatability of landfill leachate treatment with application of electrochemical oxidation followed by biological treatment of an activated sludge batch system. The electro-oxidation promotes the removal or degradation of pollutants species directly or indirectly, through processes which do not require addition of large amounts of chemicals. For tests with raw leachate and leachate with alkaline subjected to physico- chemical treatment of air stripping, there was no need to add support for electrolytes and chemical oxidation occurs over such trials the subject was measured as the COD, TOC and DOC. When applied the electro-oxidation in the raw leachate (without treatment) was reached 87% for COD removal using the DDB anode with the application of 48 L h-1 (current density 100 mA cm-2) and 65% COD removal when using the DSA anode under the same conditions. Similarly, the percentage values of TOC removal are 70 and 60 % respectively and also 61 and 67% compared to the DOC was obtained. In order to complement the studies regarding the performance of the electrochemical treatment of landfill leachate, the electro-oxidized effluent was added to an activated sludge system in two different volume ratios (2,5 and 5%) combined with sewage (97.5 and 95%, respectively). For control and possible efficiency analysis, testing with raw leachate (5% and 95 % crude leachate sanitary sewer) and only sanitary wastewater (100 %) were performed. Values of COD removal was obtained: 75% in 100% sewage condition, 64% with addition of 2,5% leachate electro- oxidized , with 57% addition of 5% leachate electro- oxidized and 38% with the addition of 5% raw leachate , and percentage values of TOC removal by about 56, 52, 47 and 37% , respectively. And BOD removal values were obtained in the order of 91, 87, 64 and 24%, respectively. In general, the proposed combined system has achieved considerable efficiency and proved to be compatible with the aim of studying the increased tractability through the use of electrochemical processes raw leachate.

O lixiviado de aterro sanitário é um efluente gerado a partir da mistura de líquidos produzidos na degradação de resíduos sólidos e a água pluvial que infiltra o depósito de material. Estudos na literatura, abordando tratamento de lixiviados de aterro sanitário, indicam que os processos biológicos podem não ser suficientes para que os padrões de lançamento vigentes na legislação sejam cumpridos. Neste contexto os processos oxidativos avançados estão sendo apontados como uma alternativa atrativa para efluentes que apresentam baixa biodegradabilidade. A presente pesquisa objetivou avaliar, em escala de bancada, a tratabilidade do lixiviado de aterro sanitário com aplicação do tratamento de oxidação eletroquímica seguida pelo tratamento biológico de um sistema de lodos ativados operado em batelada. A eletro-oxidação promove a remoção ou degradação de espécies poluentes, direta ou indiretamente, por meio de processos que não necessitam de adição de grandes quantidades de produtos químicos. Nos ensaios realizados com lixiviado bruto e com lixiviado alcalinizado submetido ao tratamento físico-químico de air stripping não houve necessidade de adicionar eletrólitos suporte para a oxidação química ocorrer e ao longo de tais ensaios a matéria foi mensurada quanto à DQO, COT e COD. Quando aplicada a eletro-oxidação no lixiviado bruto (sem tratamento prévio), houve 87% de remoção de DQO utilizando o anodo DDB com aplicação de 48 A h L-1 (densidade de corrente de 100 mA cm-2) e 65% de remoção da DQO quando utilizado o anodo DSA, nas mesmas condições. Analogamente, foram obtidos valores percentuais de remoção de COT de 70 e 60%, respectivamente e ainda 61 e 67% em relação ao COD. A fim de se complementar os estudos quanto à atuação da eletroquímica no tratamento do lixiviado de aterros sanitários, o efluente eletro-oxidado foi adicionado a um sistema de lodos ativados em duas proporções volumétricas distintas (2,5 e 5%) combinadas com esgoto sanitário (97,5 e 95%, respectivamente). Para controle e possível análise na eficiência, foram realizados ensaios com lixiviado bruto (5% de lixiviado bruto e 95% de esgoto sanitário) e somente esgoto sanitário (100%). Foram obtidos valores de remoção de DQO de: 75% em condição 100% esgoto sanitário, 64% com adição 2,5% de lixiviado eletro-oxidado, 57% com adição de 5% de lixiviado eletro-oxidado e 38% com adição de 5% de lixiviado bruto, além de valores percentuais de remoção de COT em cerca de 56, 52, 47 e 37%, respectivamente. E ainda foram obtida remoções nos valores de DBO na ordem de 91, 87, 64 e 24%, respectivamente. De forma geral, o sistema combinado proposto atingiu eficiências consideráveis e se mostrou compatível com o intuito de se estudar o aumento da tratabilidade por meio da aplicação de processos eletroquímicos em lixiviado bruto. / The landfill leachate is a wastewater generated from the mixture of liquids produced in the degradation of solid waste and rainwater that infiltrates the landfill. Studies in the literature approaching the treatment of landfill leachate indicate that biological processes may not be sufficient for the discharge standards prevailing in the present legislation. In this context the advanced oxidation processes (AOP) are being singled out as an attractive alternative for wastewater with a low biodegradability. This study aimed to evaluate, in a bench scale treatability of landfill leachate treatment with application of electrochemical oxidation followed by biological treatment of an activated sludge batch system. The electro-oxidation promotes the removal or degradation of pollutants species directly or indirectly, through processes which do not require addition of large amounts of chemicals. For tests with raw leachate and leachate with alkaline subjected to physico- chemical treatment of air stripping, there was no need to add support for electrolytes and chemical oxidation occurs over such trials the subject was measured as the COD, TOC and DOC. When applied the electro-oxidation in the raw leachate (without treatment) was reached 87% for COD removal using the DDB anode with the application of 48 L h-1 (current density 100 mA cm-2) and 65% COD removal when using the DSA anode under the same conditions. Similarly, the percentage values of TOC removal are 70 and 60 % respectively and also 61 and 67% compared to the DOC was obtained. In order to complement the studies regarding the performance of the electrochemical treatment of landfill leachate, the electro-oxidized effluent was added to an activated sludge system in two different volume ratios (2,5 and 5%) combined with sewage (97.5 and 95%, respectively). For control and possible efficiency analysis, testing with raw leachate (5% and 95 % crude leachate sanitary sewer) and only sanitary wastewater (100 %) were performed. Values of COD removal was obtained: 75% in 100% sewage condition, 64% with addition of 2,5% leachate electro- oxidized , with 57% addition of 5% leachate electro- oxidized and 38% with the addition of 5% raw leachate , and percentage values of TOC removal by about 56, 52, 47 and 37% , respectively. And BOD removal values were obtained in the order of 91, 87, 64 and 24%, respectively. In general, the proposed combined system has achieved considerable efficiency and proved to be compatible with the aim of studying the increased tractability through the use of electrochemical processes raw leachate.