Academic literature on the topic 'Advanced Photochemical Oxidation process'

The influence of H2O2 on the UV degradation of the broadly used aminopolycarboxylates EDTA and NTA in aqueous solution was investigated. The photochemical degradation in the UV /H2O2 process was compared with classical oxidative treatment of potable water. The German drinking water regulation (Trinkwasserverordnung) was the orientation for all experiments. The Advanced Oxidation Process (AOP) turned out to be superior to the classical oxidation processes. The photochemical degradation of EDTA and NTA by UV irradiation could be significantly stimulated in the presence of H2O2. There was a strong increase in the degradation rate and a decrease in the quantum yield of the aminopolycarboxylates. Experiments with butyl chloride as radical scavenger proved the photolytically generated hydroxyl radicals to be responsible for the increase in the degradation rates.The effect of increasing the degradation rate at higher concentrations of H2O2 was limited, because the steady-state concentrations of the hydroxyl radicals as reactive species, did not increase at the same rate as the initial concentration of H2O2.Low amounts of iron dissolved from the high-grade steel photoreactor walls had a significant catalytic effect on the degradation.

Studies on kinetics of galaxolide (HHCB) degradation under influence of UV, simulated sunlight and some advanced oxidation processes (H2O2, UV/H2O2, and Vis/H2O2) were conducted. Galaxolide appeared to be a photolabile compound. The first-order kinetics model was assumed for all studied processes. It was observed that basic pH favored HHCB degradation. The influence of natural matrices (river water and artificial sweat) on direct photolysis of HHCB was examined. It was stated that the process of the photodegradation proceeded slower at the presence of each matrix. HHCB lactone was identified using the GC-MS technique. The recorded chromatograms showed that apart from the lactone, other degradation products were formed that we could not identify. In order to deeper understand the HHCB degradation process, DFT calculations were performed. The results pointed out that OH radicals play a key role in HHCB decomposition, which mainly proceeds via H abstractions as well as OH additions. It follows from the calculations that the visible light is sufficient to initiate the advanced oxidation processes (AOPs) under the oxidative conditions, whereas UV irradiation is needed to start decay with no oxidative agents.

Oxytetracycline (OTC) was widely used antibiotic in agricultural industry. However, most of them were secreted from the body and entered the water stream, due to low absorption. The occurrence of the antibiotics in water stream may led to serious health hazards. Hence, finding the effective method that capable to achieve total mineralization of antibiotic-contaminated wastewater, followed by the production of benign inorganic and organic by-product, was necessarily deemed. Photochemical degradation method, such as: UV/H2O2 system, was capable to achieve total mineralization of OTC at its optimized condition. In this paper, inorganic by-products of OTC mineralization inside a UV/H2O2 system at its optimum condition were analyzed. The presence of nitrate, ammonium, chloride ions, and chlorine were detected at the sample solution after mineralization. The presence of these inorganic by-product has proven that the experimental setup chosen was capable to achieve total mineralization. In addition, possible routes of the inorganic by-products detachment from the OTC’s structure, were also presented. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

The contamination of water resources has become a significant challenge that threatens the health and well-being of people’s daily life; it calls for new technologies to be applied for water purification. Heterogeneous Fenton or Fenton-like techniques have a lot of potential as a new approach for treating wastewater because of the advantages in efficiency, safety, and economics. Various advanced oxidation processes (AOPs) are comprehensively reviewed in this work, and the •OH generation methods including chemical, electro-chemical, and photochemical approaches are summarized. Some key parameters that influence the reaction efficiency such as the temperature, catalysts, H2O2 dosage, and pH are investigated. The reaction mechanism and process optimization of photocatalysis are specifically highlighted.

Abstract Trichloroethylene, phenol, 4-cholorophenol, catechol and a pesticide were degraded by two advanced oxidation processes: photolytic oxidation with hydrogen peroxide, andphotolytic oxidation with ozone. The reactions were studied in a batch photoreactor with a low pressure mercury lamp as the radiation source. The variation of the concentration of total organic carbon with time was measured. For the organics studied, the reaction kinetics for the reduction of total organic carbon (TOC) were found to follow a power law. The exponent of the power law varies with the initial TOC concentration. Results show that TOC can be very effectively reduced provided the concentration of hydrogen peroxide used exceeds a certain threshold value. The UV/Ozone process yielded a more rapid rate of degradation and a greater degree of mineralisation.

Abstract The present work aims to study the adsorption processes and the photochemical depollution of the waters contaminated with Direct Orange textile dyes - 26 released into the water. Also, the paper shows the polysulfone (PSf) membranes, used for adsorption processes of the textile dyes azo - direct-orange-26, presenting the kinetics and experimental adsorption conditions for such processes. Advanced oxidation processes (AOP) processes used in photochemical depollution technologies are studied for water contaminated with Direct Orange 26 textile dye, after a preliminary adsorption process, with ZnFe2O4 ferrite photocatalysts.

The aim of the present work is to study a coupled system to treat biorecalcitrant wastewaters. The combination consists of an advanced oxidation process (AOP) named photo-Fenton (Ph-F), which is a photochemical treatment and a sequencing batch biofilter reactor (SBBR). The synthetic wastewater used to optimise this process is a solution of 200 ppm of 4-chlorophenol (4-CP). The first part of the work is the study of the biodegradability enhancement achieved by the photochemical process, measured as the ratio between the biochemical oxygen demand (BOD5) and the chemical oxygen demand (COD). The second step is the start-up and optimisation of the biological process. The results showed that it is necessary to severely treat the toxic solution (with 500 ppm of [H2O2]0) in order to achieve more than 90% of TOC removal in the whole process. The photochemical and biological treatments lasted 50 minutes and 24 hours, respectively.

Photocatalysis, belonging to the advanced oxidation processes (AOPs), is a potential new transformation technology for lignin derivatives to value added products (e.g., phenol, benzene, toluene, and xylene). Moreover, lignin represents the only viable source to produce aromatic compounds as fossil fuel alternative. This review covers recent advancement made in the photochemical transformation of industrial lignins. It starts with the photochemical reaction principle followed by results obtained by varying process parameters. In this context, influences of photocatalysts, metal ions, additives, lignin concentration, and illumination intensity and the influence of pH are presented and discussed. Furthermore, an overview is given on several used process analytical methods describing the results obtained from the degradation of lignin derivatives. Finally, a promising concept by coupling photocatalysis with a consecutive biocatalytic process was briefly reviewed.

A racionalização dos recursos hídricos tem sido uma das metas das indústrias em vários setores. Tais metas exigem inovações tecnológicas tanto para novos processos produtivos quanto para novas técnicas de tratamento e reutilização de água na cadeia de produção. Os custos elevados de água industrial no Brasil, particularmente nas regiões metropolitanas, têm estimulado as indústrias nacionais a avaliar as possibilidades de reúso. O objetivo deste trabalho é a aplicação do tratamento de águas de processo contendo polipropileno utilizando radiação ultravioleta e peróxido de hidrogênio, isto é, o sistema UV/H2O2, visando adequá-las para reúso no próprio processo, reduzindo a necessidade de captação de água pré-tratada e de descarte de efluente. A primeira parte do estudo consistiu na realização de experimentos em um sistema fotoquímico de batelada, empregando quatro diferentes correntes efluentes de processo, para a avaliação da viabilidade técnico-econômica do tratamento fotoquímico, bem como para a obtenção de dados referentes à cinética das reações fotoquímicas. Com base nas informações obtidas, na segunda parte do estudo foram realizados experimentos em um sistema fotoquímico contínuo, a fim de obter dados para o aumento de escala para aplicação industrial do processo de tratamento contínuo. Os resultados experimentais indicaram a viabilidade técnica de aplicação do sistema UV/H2O2 utilizando fonte de luz artificial para todas as correntes de processo estudadas, tendo sido alcançados níveis de remoção de matéria orgânica acima de 90%. No entanto, sob o ponto de vista econômico, apenas as correntes com baixo teor de carbono orgânico total dissolvido (COT), entre 6 e 12 mgC L-1, mostraram-se adequadas ao reúso, após o tratamento.
Rationalization of water use has been one of the goals in many industrial activities, and, in particular, in the petrochemical industry. Such goals demand technological innovations in the productive processes and in techniques for treatment and reuse of water in the production chain. The high costs of industrial water, particularly in some metropolitan regions, have stimulated the industries to evaluate the possibilities of water reuse. The objective of this work is to evaluate the feasibility of the UV/H2O2 photochemical process applied to the treatment of process waste water containing polypropylene, aiming at the reuse of the waste water in the as process water in the industrial complex, thus reducing the need for tap water supply and waste water generation rate. The first part of this study consisted of laboratory-scale experiments in a batch photochemical reactor with four different waste water streams to perform the technical and economical feasibility of the photochemical treatment, as well to obtain data on the degradation rate. Based on the results of the first part, the second part of this study consisted of experiments in a continuous photochemical reactor, aimed at obtaining experimental data for reactor scale-up. Experimental results indicate that the UV/H2O2 photodegradation process is able to remove more than 90% of the organic compounds contained in the waste water. However, only waste waters containing relatively low contaminant levels (between 6 and 12 mgC L-1) can be treated at economically favourable costs.

2008/2009
La nanotecnolgia rappresenta un approccio innovativo nella produzione industriale, e riflette la generale tendenza alla miniaturizzazione ed alla riduzione di scala che prevale in tutte le discipline tecnologiche. Da qui il crescente interesse nei confronti nei nanomateriali e dei materiali nanostrutturati, per lo sviluppo di nuovi prodotti innovativi e tecnologicamente avanzati, che trovino applicazione in molteplici campi. La presente tesi di dottorato si focalizza sulla strutturazione di nanomateriali a base di ossidi metallici, per applicazione come isolanti termici ad alta efficienza o come fotocatalizzatori per l’abbattimento dei contaminanti da acque reflue. Nel campo dell’isolamento termico l’attenzione è stata focalizzata su Al2O3, che, grazie alle sue uniche proprietà di tessitura, ottenute attraverso una scelta accurata delle condizioni di sintesi, ed all’elevata stabilità termica, è un materiale di forte interesse in questo settore. Lo studio della capacità di termoisolamento di materiali a base di Al2O3 ha rivelato una diretta dipendenza della diffusività e conducibilità termica dalle caratteristiche di tessitura e di struttura dell’ossido, e dalle modalità di agglomerazione. I risultati più rilevanti riscontrati nell’ambito di questa parte del lavoro hanno dato chiare indicazioni su come disegnare la strutturazione di un isolante termico: 1. Effetto del tipo di porosità presente (macro vs meso): l’aumento del contenuto di macropori determina una diminuzione del valore di conducibilità, ed un aumento di diffusività, per cui il materiale è un isolante termico; al contrario, la presenza di mesopori favorisce la riduzione di entrambe conducibilità e diffusività, per cui il materiale presenta proprietà di termoisolamento ed antifiamma; 2. Effetto del diametro dei mesopori: la modulazione del diametro dei pori a parità di porosità nella regione meso, non incide sul valore di diffusività e conducibilità, con il vantaggio che, aumentando le dimensioni, aumentano anche la resistenza meccanica e la stabilità termica dell’ossido; 3. Effetto della morfologia di assemblaggio del materiale: incide pesantemente sul trasferimento dell’energia termica, poiché, in presenza di un agglomerato hard, la conducibilità e la diffusività aumentano di un ordine di grandezza. Ne consegue che un materiale termoisolante deve avere una struttura mesoporosa ed una morfologia di tipo aggregato soft. È necessario evitare la sinterizzazione massimizzando la stabilità termica (es. mesopori di “grandi” dimensioni). L’analisi dei parametri di sintesi ha rilevato degli effetti sui processi di aggregazione nel gel-precursore di aerogel, che indirizzano in modo critico le proprietà di tessitura del prodotto finale. Il lavoro di ottimizzazione di tali parametri ha permesso di realizzare lo scale up del processo su scala industriale, da 200 ml a 25 L. La seconda parte del lavoro di ricerca è stata focalizzata sull’abbattimento di contaminanti da percolato di discarica ed acque reflue industriali per via fotocatalitica mediante processi di tipo APO. L’APO, ed in particolare la fotocatalisi con TiO2, si è rivelato un metodo di trattamento di efficiente e versatile, rendendo possibile la decontaminazione di reflui di diversa natura, dalle acque industriali al più complesso percolato di discarica. Lo studio dei parametri di processo ha evidenziato, infatti, la possibilità di semplificare il trattamento, a seconda della complessità del refluo. Mentre nel caso del percolato di discarica è necessario un trattamento con il sistema TiO2/H2O2/UV, in quanto, in virtù del sinergismo H2O2/UV, il contenuto di COD può essere portato a livelli sufficientemente bassi da permettere il completamento della decomposizione per via fotocatalitica, il refluo proveniente dall’industria del sughero può essere depurato anche in presenza del solo agente ossidante, o per effetto della sola fotocatalisi, in tempi ragionevolmente brevi rispetto a quelli richiesti per la decontaminazione del percolato (8 ore). In entrambi i casi è probabilmente possibile aumentare l’efficienza del processo mediante un’alimentazione in continuo dell’agente ossidante. In particolare, con l’approfondimento dello studio del trattamento delle acque industriali nel prototipo di reattore pilota, e la modellizzazione matematica dell’abbattimento dei contaminanti, è stato possibile parametrizzare il processo sulla base delle dimensioni dell’impianto, confermandone la fattibilità ed applicabilità su scala industriale.
XXII Ciclo
1980

Municipal wastewater treatment using biological nutrient removal generates large amounts of waste sludge. An effort is made to solubilize nutrients from sludge and reuse them in subsequent processes. The microwave-enhanced advanced oxidation (MW/H₂O₂-AOP) process using hydrogen peroxide as the oxidant was applied to the treatment of different organic slurries including wasted sludge, blood meal, and fish silage. The factors controlling phosphates, ammonia, and COD release into solution included inorganic acid addition, hydrogen peroxide dosage, treatment times and temperatures. Higher dosages and treatment temperatures yielded better solubilization of phosphates and ammonia. It was found that approximately all of the COD was solubilized at a treatment temperature of 80°C. Volatile fatty acid (VFA) concentrations were also found to have increased with the amount of inorganic acid added into treatment. Up to 25% of soluble COD was composed of acetic acid. Higher irradiation levels tended to be more effective in the solubilization of nutrients. In terms of trends of particle size distribution, detectable particles increased in size in acidic conditions, with the largest fraction of larger particles in a given sample being the treatment with highest irradiation power. In neutral condition treatments, the higher the irradiation power provided to the samples, the more spread out the particle sizes range. In alkaline condition treatments, an increase in smaller particles were found after treatment; higher power irradiation yielded significantly higher numbers of smaller particles. This study provided an insight into the athermal effects of theMW/H₂O₂-AOP. Blood meal solubilization for the purpose of its application as an organic feritilizer was investigated using theMW/H₂O₂-AOP. It was found that over the treatment temperature range of 60 to l20C, solids particle reduction, ammonia and orthophosphate production were achieved. Maximum solubility of chemical oxygen demand (COD) occurred at 80°C. Without the addition of acid, soluble COD decreased due to protein denaturation and coagulation out of the solution. Fish silage is also a valuable fertilizer for organic greenhouse hydroponics operations, but a pretreatment step is required. It was found that up to 26% of total Kjeldahl nitrogen could be released as ammonia with 6% hydrogen peroxide dosage at 170°C. An increase of nitrate/nitrite concentration was observed with higher hydrogen peroxide dosage and higher microwave temperature.

Waste activated sludge (WAS) and dairy manure (DM) present serious environmental concerns since they contain high levels of nutrients, organic matter and pathogens contained. The microwave enhanced advanced oxidation process (MW/H₂O₂-AOP) was used to treat these waste materials for solids disintegration, nutrients solubilization and pathogen destruction. For pathogen reduction, fecal coliform concentrations were found below detection limits (1000 CFU/L) immediately after treatment when sludge was treated at 70ºC with more than 0.04% of H₂O₂. Significant regrowth of fecal coliforms was observed after the treated samples were stored at ambient temperature for 72 hours. However, no regrowth was observed for samples treated at 70ºC with 0.08% H₂O₂ or higher, suggesting a complete elimination of fecal coliforms. With extracted cells that are EPS-free, orthophosphate could be released at lower microwave temperatures and lower H₂O₂ dosages, compared to our previous studies. The amount of DNA in solution was a good indicator of the extent of cell damage; the high concentration of DNA released into solution after treatment indicated significant cell damage. The effects of pre-microwave heating, microwave irradiation and post-microwave setting on nutrients and organic matters solubilization in continuous MW/H₂O₂-AOP were studied. Pre-microwave heating did not improve the overall orthophosphate solubilization, but helped in organic matter solubilization. It was beneficial to operate a continuous mode of the MW/H₂O₂-AOP at a longer retention time for organic matter solubilization, and at a shorter retention time for orthophosphate solubilization. Sludge settleability was greatly improved with the microwave treatment, with or without the addition of H₂O₂. It was found that 69 to 92% of the TP and up to 90% of TCOD in DM were in the soluble form, after continuous MW/H₂O₂-AOP with an exit temperature of 90oC and acid dosage of 1.0% (vol/vol). Acid addition was important in phosphate solubilization but the dosage of acid affect the solubilization to a lesser extent. For organic matter solubilization, acid played an important role – SCOD release increased with the increase of acid dosage. Higher microwave exit temperature resulted in higher SCOD and ortho-P solubilization.

El bisfenol A (BPA) i la tartrazina (TAR) pertanyen al grup de compostos que són potencialment nocius per a la recuperació d'aigües residuals. El BPA és un disruptor del sistema hormonal o disruptor endocrí, mentre que la TAR és un colorant azoic. Una diversitat d'indústries, especialment la indústria paperera i tèxtil, produeixen un gran volum d'aigües residuals que estan contaminades amb BPA i colorants. Per tant, els efluents que contenen tant BPA com colorants han de ser gestionats de manera eficient amb la finalitat d'evitar problemes ambientals vinculats a ells. Durant l'última dècada, s’han assajat diversos mètodes per a l'eliminació de BPA i TAR d'aigües residuals, resultant ser eficaços i potencialment aplicables a gran escala. No obstant això, la majoria d'ells encara enfronten problemes de costos, la qual cosa exigeix el seu desenvolupament. La nanofiltració (NF) ofereix una solució adequada per a l'eliminació de BPA i colorants de les solucions aquoses, degut a la seva capacitat per retenir substàncies orgàniques dissoltes. És per això que en aquest treball de tesi, es va utilitzar la NF en flux tangencial mitjançant membranes polimèriques per eliminar BPA i TAR de solucions aquoses. Addicionalment, la degradació de BPA i TAR durant els tractaments per Fenton, ozonación i enzimàtic sota diferents condicions d'operació, en combinació amb la seva posterior NF van ser assajats. Resultats indiquen que tant el BPA com la TAR poden ser eficientment degradats per aquests processos. L'ús d'un sistema integrat membrana-reactor va mostrar el potencial i les limitacions de l'ús dels processos d'oxidació avançada en conjunt amb membranes de NF per a la remoció del BPA i de la TAR. En general elevades eficiències de remoció van ser aconseguides amb les diferents membranes de NF utilitzades.
Bisfenol A (BPA) y tartrazina (TAR) pertenecen al grupo de compuestos que son potencialmente dañinos para la recuperación de aguas residuales. BPA es un perturbador del sistema hormonal o disruptor endocrino, mientras que la TAR es un colorante azo. Variedad de industrias, especialmente la industria papelera y textil producen un gran volumen de aguas residuales que están contaminadas con BPA y colorantes. Por lo tanto, los efluentes que contiene tanto BPA como colorantes, deben ser gestionados de manera eficiente con la finalidad de evitar problemas ambientales vinculados a ellos. Durante la última década, varios métodos para la eliminación de BPA y TAR de aguas residuales han sido probados, resultando ser eficaces y potencialmente aplicables a gran escala. Sin embargo, la mayoría de ellos todavía enfrentan problemas de costes, lo cual exige su desarrollo. La nanofiltración (NF) ofrece una solución adecuada para la eliminación de BPA y colorantes de las soluciones acuosas debido a su capacidad para remover sustancias orgánicas disueltas. Es por ello que en esta tesis, la NF en flujo cruzado usando membranas poliméricas fue utilizada para remover BPA y TAR de soluciones acuosas. Adicionalmente, la degradación de BPA y TAR durante los tratamientos por Fenton, ozonación y enzimático bajo diferentes condiciones de operación, en combinación con su posterior NF fueron ensayados. Resultados indican que tanto el BPA como la TAR pueden ser eficientemente degradados por estos procesos. El uso de un sistema integrado membrana-reactor mostró el potencial y las limitaciones del uso de los procesos de oxidación avanzada en conjunto con membranas de NF para la remoción del BPA y de la TAR. En general elevadas eficiencias de remoción fueron alcanzadas con las diferentes membranas de NF utilizadas.
Bisphenol A (BPA) and tartrazine (TAR) belong to the compounds which are potentially harmful during wastewater reclamation. BPA is a typical Endocrine Disrupting Chemical and TAR is an azo dye. Variety of industry, especially paper and textile industries produces a large volume of wastewater that is polluted with BPA and dyes. Therefore, BPA and dyes-charged effluents need to be efficiently managed in order to avoid environmental problems linked to them. During the last decade, several methods for BPA and TAR removal of wastewater have been found effective and potentially applicable for scaling up. However, most of them still face cost problems, thus demanding further development. It is generally accepted that nanofiltration (NF) offers an adequate solution for the removal of BPA and dyes from the aqueous solutions owing to its capacity to remove dissolved organics. In the present thesis, crossflow NF using thin film composite polymeric membranes were applied to reject BPA and TAR from aqueous solutions. Additionally, the degradation of BPA and TAR during Fenton’s, ozonation and enzymatic processes under different operational conditions, in combination with subsequent NF of low concentration remnant BPA and TAR and compounds derived from oxidation was investigated. Results indicate that BPA and TAR could be degraded efficiently in aqueous phase by Fenton, ozonation and enzymatic processes. The use of a membrane-reactor integrated system for BPA and TAR degradation demonstrated the potential and limitations of using advance oxidation processes, operated in a recycling mode coupled to a NF membrane. In general, high BPA and TAR removal efficiencies for several NF membranes were achieved.

En cuanto a la mejora de los Procesos de Oxidación Avanzada para el tratamiento de aguas residuales, se han diseñado y estudiado nuevos procesos catalíticos Fenton y ozonización catalítica para la eliminación de contaminantes orgánicos del agua. El proceso Fenton se ha realizado mediante peróxido de hidrógeno generado in situ, el cual se ha producido a partir de ácido fórmico y oxígeno sobre un catalizador de paladio soportado en alúmina. A continuación, se ha heterogeneizado totalmente el sistema utilizando un catalizador bimetálico Pd-Fe y se ha aplicado con éxito en la degradación de diferentes categorías de contaminantes orgánicos. La combinación de este proceso de oxidación con hidrodecloración ha obtenido una alta eficiencia en la degradación de clorofenoles. En cuanto al uso de diferentes sustitutos de H2, se ha observado una mayor eficiencia de la hidroxilamina en el proceso Fenton con generación in situ de peróxido de hidrógeno para efluentes neutros. Con respecto al desarrollo de nuevos materiales para ozonización catalítica, se ha estudiado la degradación de compuestos farmacéuticos mediante catalizadores de cobre-dawsonita. El cobre incorporado en la estructura de dawsonita presenta una mayor actividad en la ozonización catalítica con respecto a la muestra calcinada, cobre en solución y óxido de cobre soportado en alúmina.
Regarding to the improvement of Advanced Oxidation Processes for wastewater treatment, new catalytic Fenton process and catalytic ozonation were designed and studied in the removal of organic pollutants from water. Fenton process was performed using in situ generated hydrogen peroxide, which was produced from formic acid and oxygen over alumina-supported palladium catalyst. Then, the system was fully heterogenized by using bimetallic Pd-Fe catalyst and applied successfully for different categories of organic pollutants. The combination of the above oxidation process with hydrodechlorination led to high efficiency in the degradation of chlorophenols. The performance of different hydrogen substitutes in the Fenton process using in situ generated hydrogen peroxide showed higher efficiency of hydroxylamine for neutral solutions. Concerning the development of new catalytic materials for catalytic ozonation, the degradation of pharmaceutical compounds was performed using dawsonite-derived copper catalysts. The copper incorporated into the structure of dawsonite indicated higher activity in catalytic ozonation with respect to the calcined sample, soluble copper and aluminasupported copper oxide.

The objective of this thesis is contributing to the development of a systematic modelling approach for a more efficient and sustainable water management. The main aim is introducing Chemical and Process System Engineering methods and tools to provide a contribution to the AOPs (Advanced Oxidation Processes) investigation field by proposing process models that can be exploited to progress towards efficient management strategies for practical AOPs operation and inclusion in wastewater treatment networks. First, different advanced oxidation processes, namely Fenton, photo-Fenton and VUV photo-oxidation, were investigated and compared for the treatment of paracetamol (PCT) aqueous solution, by evaluating a series of performance indicators. Among the selected AOPs, VUV photo-oxidation and photo-Fenton showed the most promising results. Both processes allowed attaining total removal of the target compound and high mineralization levels. The second and main part of the thesis was focused on transforming “data into knowledge” by proposing different modelling approaches. The modelling effort focused on Fenton/photo-Fenton processes that showed the need of improving operating conditions. Accordingly, two practical kinetic models for Fenton and photo-Fenton degradation of organic compounds have been proposed and validated: • A conventional First Principles Model, based on a line source radiation model with spherical and isotropic emission, developed for the prediction of Fenton and photo-Fenton degradation of PCT and the oxidant (H2O2) consumption; • A general non-conventional First Principles Model, based on a wide-ranging contaminant degradation mechanism considering a variable number of carbon atoms for the characterization of the intermediates. Both models were experimentally validated and showed that were able to satisfactorily reproduce the system behavior. Particularly, the non-conventional First Principles Model showed to be a successful modelling approach for the Fenton/photo-Fenton degradation of different wastewater systems composed by single or multiple organic contaminants by means of lumped parameters (e.g. Total Organic Carbon-TOC). Thus, the approach proved to offer practical characterization of complex mixtures of chemicals. Once process models are proposed and validated, they can be systematically exploited to determine efficient operation modes or design alternatives. Accordingly, the thesis addressed two cases of practical interest: the optimization of a control recipe and the design of a treatment network. Particularly, a dynamic optimization framework for taking advantage of available kinetic models and determining the best hydrogen peroxide dosage profile, was proposed. Economic and environmental objectives and constraints were included to develop a dynamic optimization problem that was implemented in JModelica and solved using a direct simultaneous optimization method (IPOPT). Finally, the combination of cheaper conventional biological processes with more expensive AOPs was explored. A Mixed-Integer Non Linear Programming (MINLP) model for the optimization of a general wastewater network was proposed based on a superstructure of alternative designs, which was implemented and solved in GAMS. The novel formulation includes the BOD5/COD ratio method, describing the removal efficiency of BOD5 and COD of a treatment for modelling the variation of the biodegradability of the influents. This novel formulation allows determining the extent of the AOP treatments when combined with biological treatments, and paves the way for more complex models aimed at solving the trade-off between cost and treatment efficiency.
El objetivo de esta tesis es contribuir al desarrollo de técnicas de modelado sistemático para una gestión del agua eficiente y sostenible. El objetivo principal es contribuir a la investigación de los PAOs (Procesos Avanzados de Oxidación). La tesis introduce métodos y herramientas de Ingeniería de Procesos Químicos y propone modelos que puedan ser explotados para producir estrategias eficientes de gestión y operación de los PAOs, así como para la integración de estos PAOs en redes de tratamiento de aguas residuales. Primero, se investigaron diferentes PAOs. Se consideraron los procesos Fenton, foto-Fenton y la foto-oxidación VUV, y se compararon en el tratamiento de soluciones acuosas de paracetamol (PCT) adoptando una serie de indicadores de rendimiento (Key Performance Indicators, KPI). Entre los PAOs seleccionados, la foto-oxidación VUV y foto-Fenton producieron los resultados más prometedores, permitiendo lograr la eliminación total del contaminante y alto nivel de mineralización. La segunda parte de la tesis se centró en transformar ¿datos en conocimiento¿ mediante la propuesta de modelos para los procesos Fenton / photo-Fenton con el fin de mejorar las condiciones operativas de los mismos. En concreto se han propuesto y validado dos modelos cinéticos que describen la degradación de compuestos orgánicos por procesos Fenton y foto-Fenton: ¿ Un Modelo de Principios Básicos (F convencional, que incluye la modelización de la radiación lineal con emisión esférica e isotrópica, desarrollado para predecir la degradación Fenton y foto-Fenton del PCT y el consumo de oxidante (H2O2); ¿ Un Modelo de Principios Básicos no convencional, que propone un mecanismo de degradación de contaminantes general puesto que considera el número de átomos de carbono del contaminante como la variable de partida para la propuesta de fragmentación y consiguiente generación de intermedios. Ambos modelos se validaron experimentalmente y mostraron reproducir satisfactoriamente el comportamiento del sistema. En particular, el Modelo de Principios Básicos no convencional genero resultados prometedores para la degradación Fenton / foto-Fenton de diferentes sistemas (compuestos por uno o más contaminantes orgánicos) por medio de parámetros globales (como el Carbono Orgánico Total). Por tanto, este enfoque ofrece un modelado práctico independiente del contaminante y válido para mezclas complejas de productos químicos. Una vez propuestos y validados, los modelos de proceso se pueden utilizar sistemáticamente para determinar modos de operación eficientes o alternativas de diseño. En consecuencia, la tesis se dirigió a dos casos de interés práctico: la optimización de una receta de control y el diseño de una red de tratamiento. En el primer caso, se propuso una estrategia de optimización dinámica para aprovechar los modelos cinéticos disponibles y determinar el mejor perfil de dosificación de peróxido de hidrógeno. Se incluyeron objetivos y limitaciones económicas y ambientales para desarrollar un problema de optimización dinámica que se implementó en JModelica y se resolvió utilizando un método de optimización simultánea directa (IPOPT). Finalmente, se exploró la combinación de procesos biológicos convencionales, más baratos, con PAOs, más costosos. Se propuso un modelo de Programación no Lineal de Enteros Mixtos (MINLP) para la optimización de una red general de aguas residuales, basado en una superestructura de diseños alternativos, que se implementó y resolvió en GAMS. La nueva formulación incluye la relación BOD5 / COD, que describe la eficiencia de eliminación de BOD5 y COD de un tratamiento con el fin de modelar la variación de la biodegradabilidad de los influentes. Esta novedosa formulación permite determinar el alcance de los tratamientos de PAOs cuando se combinan con tratamientos biológicos, y allana el camino para modelos más complejos destinados a resolver el equilibrio entre coste y eficiencia del tratamiento.
L'objectiu d'aquesta tesi és contribuir al desenvolupament de tècniques de modelatge sistemàtic per a una gestió de l'aigua eficient i sostenible. L'objectiu principal és contribuir a la investigació dels PAOs (Processos Avançats d'Oxidació). La tesi introdueix mètodes i eines d'Enginyeria de Processos Químics i proposa models que puguin ser explotats per produir estratègies eficients de gestió i operació dels PAOs, així com per a la integració d'aquests PAOs en xarxes de tractament d'aigües residuals. Primer, es van investigar diferents PAOs. Es van considerar els processos Fenton, foto-Fenton i la foto-oxidació VUV, i es van comparar en el tractament de solucions aquoses de paracetamol (PCT) adoptant una sèrie d'indicadors de rendiment (Key Performance Indicators, KPI). Entre els PAOs seleccionats, la foto-oxidació VUV i foto-Fenton van produir els resultats més prometedors, permetent aconseguir l'eliminació total del contaminant i alt nivell de mineralització. La segona part de la tesi es va centrar en transformar "dades en coneixement" mitjançant la proposta de models per als processos Fenton / photo-Fenton amb la finalitat de millorar les condicions operatives dels mateixos. En concret, s’han proposat i validat dos models cinètics que descriuen la degradació de compostos orgànics per processos Fenton i foto-Fenton: • Un model de Principis Bàsics convencional, que inclou la modelització de la radiació lineal amb emissió esfèrica i isotròpica, desenvolupat per predir la degradació Fenton i foto-Fenton del PCT i el consum d'oxidant (H2O2); • Un model de Principis Bàsics no convencional que proposa un mecanisme de degradació de contaminants general, ja que considera el nombre d'àtoms de carboni del contaminant com la variable de partida per a la proposta de fragmentació i consegüent generació d'intermedis. Tots dos models es van validar experimentalment i van mostrar la seva capacitat de reproduir satisfactòriament el comportament del sistema. En particular, el Model de Principis Bàsics no convencional ha generat resultats prometedors per a la degradació Fenton / foto-Fenton de diferents sistemes (compostos per un o més contaminants orgànics) per mitjà de paràmetres globals (com el Carboni Orgànic Total). Per tant, aquest enfocament ofereix un modelatge pràctic, independent del contaminant i vàlid per a mescles complexes de productes químics. Un cop proposats i validats, els models de procés es poden utilitzar sistemàticament per determinar maneres d'operació eficients o alternatives de disseny. En conseqüència, la tesi es va dirigir a dos casos d'interès pràctic: l'optimització d'una recepta de control i el disseny d'una xarxa de tractament. En el primer cas, es va proposar una estratègia d'optimització dinàmica per aprofitar els models cinètics disponibles i determinar el millor perfil de dosificació de peròxid d'hidrogen. Es van incloure objectius i limitacions econòmiques i ambientals per desenvolupar un problema d'optimització dinàmica que es va implementar en JModelica i es va resoldre utilitzant un mètode d'optimització simultània directa (IPOPT). Finalment, es va explorar la combinació de processos biològics convencionals, més barats, amb PAOs, més costosos. Es va proposar un model de Programació No Lineal Entera Mixta (MINLP) per a l'optimització d'una xarxa general d'aigües residuals, basat en una superestructura de dissenys alternatius, que es va implementar i resoldre en GAMS. La nova formulació inclou la relació BOD5 / COD, que descriu l'eficiència d'eliminació de BOD5 i COD d'un tractament per tal de modelar la variació de la biodegradabilitat dels influents. Aquesta nova formulació permet determinar l'abast dels tractaments de PAOs quan es combinen amb tractaments biològics, i aplana el camí per a models més complexos destinats a resoldre l'equilibri entre cost i eficiència del tractament.
L'obiettivo della presente tesi è contribuire allo sviluppo di tecniche di modellizzazione sistematica finalizzate ad una gestione efficiente e sostenibile delle risorse idriche. L'obiettivo principale è contribuire allo studio dei POA (Processi di Ossidazione Avanzata). La tesi introduce metodi e strumenti dell’ingegneria dei processi chimici e propone modelli che possano servire per lo sviluppo di strategie efficaci di gestione dei POA nonché per l'integrazione di questi ultimi nelle reti di trattamento delle acque reflue. In primo luogo, sono stati studiati diversi POA. Nello specifico, sono stati studiati i processi di foto-ossidazione Fenton, photo-Fenton e VUV per il trattamento di soluzioni acquose di paracetamolo (PCT) la cui efficacia è stata confrontata adottando una serie di indicatori di prestazione (Key Performance Indicators, KPI). Tra i POA selezionati, la foto-ossidazione VUV e il processo photo-Fenton hanno prodotto i risultati più promettenti, consentendo di ottenere l'eliminazione totale del contaminante e un alto livello di mineralizzazione. La seconda parte della tesi si è concentrata sulla trasformazione dei "dati in conoscenza" proponendo modelli finalizzati alla descrizione dei processi Fenton / photo-Fenton e con l’obiettivo ultimo di adoperarli per ottimizzare le condizioni operative di questi ultimi. In particolare, sono stati proposti e validati due modelli cinetici che descrivono la degradazione dei composti organici per mezzo dei processi Fenton e photo-Fenton: • Un modello convenzionale, che include la modellizzazione della radiazione basata sull’ipotesi di radiazione lineare ed emissione sferica e isotropica, e in grado di prevedere la degradazione del PCT ad opera dei processi Fenton e photo-Fenton nonché il consumo di ossidante (H2O2); • Un modello non convenzionale, che propone un meccanismo generale di degradazione degli inquinanti basato sul numero di atomi di carbonio del contaminante da degradare a partire dal quale si propone un meccanismo di frammentazione di quest’ultimo con conseguente generazione di prodotti intermedi. Entrambi i modelli sono stati validati sperimentalmente e hanno mostrato prestazioni soddisfacenti. In particolare, il modello non convenzionale ha mostrato di poter rappresentare la degradazione Fenton e photo-Fenton di diversi composti organici attraverso l’utilizzo di un parametro globale (come il carbonio organico totale) e qindi di offrire una proposta di modellizzazione pratica indipendente dal contaminante e che può pertanto essere adottata in caso di miscele complesse di prodotti chimici. Una volta proposti e convalidati, i modelli di processo possono essere utilizzati sistematicamente per determinare modalità operative efficienti o alternative di progettazione. Di conseguenza, la tesi ha affrontato due casi di interesse pratico: l'ottimizzazione della ricetta di controllo del processo e la progettazione di una rete di trattamento di acque reflue. Nel primo caso è stata proposta una strategia di ottimizzazione dinamica per sfruttare i modelli cinetici disponibili e determinare il miglior profilo di dosaggio del perossido di idrogeno. Sono stati inclusi obiettivi e limiti economici e ambientali per sviluppare un problema di ottimizzazione dinamica implementato in JModelica che è stato risolto utilizzando un metodo di ottimizzazione simultanea diretta (IPOPT). Infine, è stata esplorata la combinazione di processi biologici convenzionali, più economici, con i PAO, più costosi. È stato proposto un modello MINLP (Nonlinear Mixed Integer Programming) per l'ottimizzazione di una rete di acque reflue, basato su una struttura attraverso la quale è possibile rappresentare scelte progettuali alternative, che è stato implementato e risolto in GAMS. La nuova formulazione include il rapporto BOD5 / COD, che descrive l'efficienza di eliminazione di BOD5 e COD di un trattamento al fine di modellare la variazione della biodegradabilità degli influenti. Questa nuova formulazione consente di determinare le diverse possibilità di combinazione dei PAO con i trattamenti biologici e apre la strada a modelli più complessi volti a risolvere l'equilibrio tra costo ed efficienza del trattamento.

Dairy manure treatment, using solid-liquid separation and microwave enhanced advanced oxidation process (MW/H₂O₂-AOP), was investigated. The objectives of the research were to determine: 1) the nutrient and metal composition of solid and liquid fractions of raw dairy manure following solid-liquid separation, 2) the effects of MW/H₂O₂-AOP operating factors of temperature, hydrogen peroxide (H₂O₂) dosage, acid concentration and heating time on sugar production and nutrient release from solid dairy manure. Solid-liquid separation of raw dairy manure, using a 1mm laboratory sieve, showed that solid fractions had a higher composition of TS and volatile solids (VS), while the liquid fractions were richer in nutrients and metals. Laboratory separation by screening alone was not effective in removing high amounts of nutrients and solids from the raw manure. Screening experiments were conducted using cellulose fibers to study the effects of temperature, acid concentration, H₂O₂ dosage and heating time on sugar production, with the aim of applying the results to dairy manure lignocellulosic material. Sugar production increased when acid concentration was increased from 1% to 3%, but decreased with an increase to 10%. More sugar was produced at 160°C compared to 120°C. Sugar production decreased with increasing time. Microwave irradiation of solid dairy manure at pH 2, temperatures of 80, 120 and 160°C, H₂O₂ dosages of 0 to 0.50 mL, and heating times of 10 to 20 min, showed that more sugars were released at higher temperatures. Temperature and hydrogen peroxide dosage were identified as the most important factors affecting solubilization of phosphorus and ammonia. Subsequently, a two-stage acid hydrolysis process, using MW/H₂O₂-AOP, was used to investigate sugar production and solubilization of phosphorus and ammonia from solid dairy manure at: 3% acid concentration, 120 and 160°C, 0 and 2 mL H₂O₂ and heating times of 20 and 60min. To enhance sugar production from solid dairy manure, the microwave should be operated at higher temperatures and shorter heating times with no H₂O₂. For ammonia and phosphorus solubilization, higher temperatures and longer heating times, in the presence of H₂O₂, would be advantageous. MW/H₂O₂-AOP is therefore an efficient means for treating diary manure for nutrient recovery.

Anaerobic digestion (AD) of dairy manure is an alternative to traditional manure management using land application. There are many benefits of AD but it is currently not an economically viable option in many parts of North America. The focus of this investigation was to determine whether liquid dairy manure treated by microwave hydrogen peroxide advanced oxidation process (MW/H₂O₂-AOP) would increase the anaerobic biodegradability of the substrate, producing higher methane yields. Biochemical methane potential (BMP) tests were conducted to measure biogas generation and the Modified Gompertz equation was used to determine the kinetics of anaerobic biodegradability. The research found that MW/H₂O₂-AOP was effective in solubilizing nutrients and organics in liquid dairy manure, but it does not necessarily translate into enhanced anaerobic biodegradability. The BMP tests revealed that digestion of untreated dairy manure at 35ºC had the highest methane yields. Severe inhibition was observed for the digestion of acidified dairy manure. This was attributed to sulfide inhibition. In addition, ammonia concentrations were suspected as the main reason for severe inhibition of microwave treated dairy manure with no acid addition, but a number of other factors could also be responsible, including sulfide, light metals and lack of temperature acclimation for inoculum. Pretreatment of sewage sludge and BMP tests were also conducted to compare the effect of MW/H₂O₂-AOP with dairy manure. The results showed that the microwave treatment had a positive impact on anaerobic digestibility of sewage sludge, especially for mesophilic digestion. At 35ᵒC, MW alone generated the highest methane yields followed by MW/H₂O₂ and then the control. In terms of methane yield, microwave treatment improved the methane production rate for mesophilic digestion, but not thermophilic digestion. The positive results for BMP tests of microwave treated sewage sludge suggest that the influence of microwave treatment on anaerobic biodegradability is substrate and solid concentration specific. There was no clear and consistent increase or decrease in soluble metal (Ca, K, Mg, Na) concentrations after MW/H₂O₂-AOP. However, it was found that acidified treatment was effective in releasing calcium and magnesium into solution. After digestion, the soluble calcium, potassium, magnesium and sodium content of dairy manure was reduced.

The decontamination factor of liquid waste containing 60Co is generally weak. This is due to the presence of complexant molecules. For instance, complexation of EDTA with 60Co decreases efficiency of radioactive waste treatment. The aim of this study was to degrade EDTA in H2O and CO2 and to concentrate free 60Co in order to increase decontamination factor. A first test of radioactive waste treatment by photocatalysis was allowed to increase decontamination factor (60Co) from 16 to 196 with a device requiring to be improved. The present work concerns the first step of the degradation process development with a more powerful device. These first experiments were leaded to follow the only EDTA oxidation. EDTA degradation was carried out by the following Advanced Oxidation Processes (AOP): UV/H2O2 (photochemistry); UV/TiO2 (photocatalysis); UV/TiO2/H2O2. A specific reactor was achieved for this study. The wavelength used was 254 nm (UVC). The photocatalytic degradation of EDTA was carried out with Degussa P-25 titanium dioxide (TiO2), which is a semiconductor photocatalyst. The degradation degree of EDTA and the intermediate products were monitored by TOC and ionic chromatography methods. The effects of various parameters such as pH and the quantity of H2O2 were studied. This allows us to conclude that basic pH slows down EDTA degradation. The study showed that UV/H2O2 process was the most effective treatment process under acid conditions. The rate of EDTA degradation was very high and reached 95% in 120 minutes. The presence of glyoxilic, oxalic, glycolic and formic acids was detected as degradation products. Among the intermediates produced by photochemistry, NO3− ions presence informed of the amine degradations. These results highlighted faster EDTA degradation by photochemistry than photocatalysis.

Light capturing and energy conversion by PSI is one of the most fundamental processes in nature. In the heart of these adaptations stand PSI, PSII and their light harvesting antenna complexes. The main goal of this grant proposal was to obtain by X-ray crystallography information on the structure of plant photosystem I (PSI) and photosystem II (PSII) supercomplexes. We achieved several milestones along this line but as yet, like several strong laboratories around the world, we have no crystal structure of plant PSII. We have redesigned the purification and crystallization procedures and recently solved the crystal structure of the PSI supercomplex at 3.3 Å resolution. Even though this advance in resolution appears to be relatively small, we obtained a significantly improved model of the supercomplex. The work was published in J. Biol. Chem. (Amunts et al., 2010). The improved electron density map yielded identification and tracing of the PsaK subunit. The location of an additional 10 ß-carotenes, as well as 5 chlorophylls and several loop regions that were previously uninterruptable have been modeled. This represents the most complete plant PSI structure obtained thus far, revealing the locations of and interactions among 17 protein subunits and 193 non-covalently bound photochemical cofactors. We have continued extensive experimental efforts to improve the structure of plant PSI and to obtain PSII preparation amenable to crystallization. Most of our efforts were devoted to obtain well-defined subcomplexes of plant PSII preparations that are amenable to crystallization. We studied the apparent paradox of the high sensitivity of oxygen evolution of isolated thylakoids while BBY particles exhibit remarkable resilience to the same treatment. The integrity of the photosystem II (PSII) extrinsic protein complement as well as calcium effects arise from the Ca2+ atom associated with the site of photosynthetic water oxidation were investigated. This work provides deeper insights into the interaction of PsbO with PSII. Sight-directed mutagenesis indicated the location of critical sites involved in the stability of the water oxidation reaction. When combined with previous results, the data lead to a more detailed model for PsbO binding in eukaryotic PSII.

The aim of this research project was to obtain information on the role of the cytochrome b559 in the function of Photosystem-II (PSII) with special emphasis on the light induced photo inactivation of PSII and turnover of the photochemical reaction center II protein subunit RCII-D1. The major goals of this project were: 1) Isolation and sequencing of the Chlamydomonas chloroplast psbE and psbF genes encoding the cytochrome b559 a and b subunits respectively; 2) Generation of site directed mutants and testing the effect of such mutation on the function of PSII under various light conditions; 3) To obtain further information on the mechanism of the light induced degradation and replacement of the PSII core proteins. This information shall serve as a basis for the understanding of the role of the cytochrome b559 in the process of photoinhibition and recovery of photosynthetic activity as well as during low light induced turnover of the D1 protein. Unlike in other organisms in which the psbE and psbF genes encoding the a and b subunits of cytochrome b559, are part of an operon which also includes the psbL and psbJ genes, in Chlamydomonas these genes are transcribed from different regions of the chloroplast chromosome. The charge distribution of the derived amino-acid sequences of psbE and psbF gene products differs from that of the corresponding genes in other organisms as far as the rule of "positive charge in" is concerned relative to the process of the polypeptide insertion in the thylakoid membrane. However, the sum of the charges of both subunits corresponds to the above rule possibly indicating co-insertion of both subunits in the process of cytochrome b559 assembly. A plasmid designed for the introduction of site-specific mutations into the psbF gene of C. reinhardtii. was constructed. The vector consists of a DNA fragment from the chromosome of C. reinhardtii which spans the region of the psbF gene, upstream of which the spectinomycin-resistance-conferring aadA cassette was inserted. This vector was successfully used to transform wild type C. reinhardtii cells. The spectinomycin resistant strain thus obtained can grow autotrophically and does not show significant changes as compared to the wild-type strain in PSII activity. The following mutations have been introduced in the psbF gene: H23M; H23Y; W19L and W19. The replacement of H23 involved in the heme binding to M and Y was meant to permit heme binding but eventually alter some or all of the electron transport properties of the mutated cytochrome. Tryptophane W19, a strictly conserved residue, is proximal to the heme and may interact with the tetrapyrole ring. Therefore its replacement may effect the heme properties. A change to tyrosine may have a lesser affect on the potential or electron transfer rate while a replacement of W19 by leucine is meant to introduce a more prominent disturbance in these parameters. Two of the mutants, FW19L and FH23M have segregated already and are homoplasmic. The rest are still grown under selection conditions until complete segregation will be obtained. All mutants contain assembled and functional PSII exhibiting an increased sensitivity of PSII to the light. Work is still in progress for the detailed characterization of the mutants PSII properties. A tobacco mutant, S6, obtained by Maliga and coworkers harboring the F26S mutation in the b subunit was made available to us and was characterized. Measurements of PSII charge separation and recombination, polypeptide content and electron flow indicates that this mutation indeed results in light sensitivity. Presently further work is in progress in the detailed characterization of the properties of all the above mutants. Information was obtained demonstrating that photoinactivation of PSII in vivo initiates a series of progressive changes in the properties of RCII which result in an irreversible modification of the RCII-D1 protein leading to its degradation and replacement. The cleavage process of the modified RCII-D1 protein is regulated by the occupancy of the QB site of RCII by plastoquinone. Newly synthesized D1 protein is not accumulated in a stable form unless integrated in reassembled RCII. Thus the degradation of the irreversibly modified RCII-D1 protein is essential for the recovery process. The light induced degradation of the RCII-D1 protein is rapid in mutants lacking the pD1 processing protease such as in the LF-1 mutant of the unicellular alga Scenedesmus obliquus. In this case the Mn binding site of PSII is abolished, the water oxidation process is inhibited and harmful cation radicals are formed following light induced electron flow in PSII. In such mutants photo-inactivation of PSII is rapid, it is not protected by ligands binding at the QB site and the degradation of the inactivated RCII-D1 occurs rapidly also in the dark. Furthermore the degraded D1 protein can be replaced in the dark in absence of light driven redox controlled reactions. The replacement of the RCII-D1 protein involves the de novo synthesis of the precursor protein, pD1, and its processing at the C-terminus end by an unknown processing protease. In the frame of this work, a gene previously isolated and sequenced by Dr. Pakrasi's group has been identified as encoding the RCII-pD1 C-terminus processing protease in the cyanobacterium Synechocystis sp. PCC 6803. The deduced sequence of the ctpA protein shows significant similarity to the bovine, human and insect interphotoreceptor retinoid-binding proteins. Results obtained using C. reinhardtii cells exposes to low light or series of single turnover light flashes have been also obtained indicating that the process of RCII-D1 protein turnover under non-photoinactivating conditions (low light) may be related to charge recombination in RCII due to back electron flow from the semiquinone QB- to the oxidised S2,3 states of the Mn cluster involved in the water oxidation process.