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The presence of emerging contaminants (ECs) in water and wastewater systems has become a subject of significant concern worldwide. These emerging contaminants are complex organic molecules which potentially affect human health and environment. Conventional wastewater treatment plants are unable to completely remove these contaminants from water and therefore can discharge them into environment. The need to develop effective methods for ECs removal is essential. This study assess the potential of ozone based advanced oxidation processes (AOP) to oxidize number of emerging contaminants. Different combinations of ozone with hydrogen peroxide and sodium persulfate were tested. For this study 1-4, dioxane, perfluorinated compounds (PFCs), N,N-Diethyl-metatoluamide, and three pharmaceuticals sulfamethoxazole, trimethoprim and carbamazepine have been selected. The effect of different process parameters such as chemical dosages, ozone weight percent, ozone flow rates, etc. on destruction of ECs were examined. It was observed that 1, 4-dioxane were persistent to direct ozone reaction, however were easily oxidized by hydroxyl radical. However, ozonation was solely very effective (> 99 %) in removing pharmaceuticals such as sulfamethoxaole, trimethoprim and carbamazepine. It was not very efficient for the removal of perfluorinated compound and N,N-Diethylmeta-toluamide. The operational conditions were optimized for maximum removal of every compound and their influence on the degradation process is discussed. / Civil Engineering

Clean water is essential to life. Growth in world population, changing diets, and a warming climate are driving an increase in the demand for water. Better management of water resources will help prevent scarcity, but in order to fully meet the future demand for safe, clean drinking water, new water treatment technologies are needed. This dissertation investigates a technology which is not well understood; the combination of ozone and ultrasound as potentially an efficient technology. Since nearly all previously published studies of combined ozone/ultrasound utilized batch reactors, a continuous flow reactor was constructed for this research. 1,4-Dioxane, henceforth referred to as dioxane, was chosen to evaluate the effectiveness of the combined ozone/ultrasound process. Dioxane is commonly detected in surface and groundwater and is a suspected human carcinogen. A recalcitrant contaminant, it resists direct oxidation by chlorine, oxygen, ozone, and biological treatment. It is miscible in water and doesn't sorb readily to organic matter, so it spreads rapidly in groundwater contamination plumes. It also resists air stripping and filtration, including reverse osmosis. For these reasons, dioxane makes an excellent candidate to measure the effectiveness of advanced oxidation processes, such as combined ozone/ultrasound. The treatment of dioxane by advanced oxidation processes has been studied extensively in the past. However, only one study has been published using combined ozone/ultrasound, and it was done in a batch reactor operating at a high ultrasonic frequency. The reactor built for this study also permitted reactor pressurization effects to be studied in a manner that has not been reported before for the combined ozone/ultrasound process. In this study, the combination of ozone and ultrasound was found to cause synergistic removal of dioxane from drinking water; the removal achieved by the combination significantly exceeded the sum of the removal achieved by ozone and ultrasound separately. In fact, the combination of ozone and ultrasound was found to remove more than double the dioxane that would be removed by doing both treatment processes separately. Ultrasound (20 kHz) was ineffective in removing dioxane alone, achieving less than 20% removal. At 16 mg/L, ozone alone was found to achieve removal of up to 86% after a 16 minute treatment time, but appears sensitive to matrix effects, especially pH. When ultrasound was combined with just 1.2 mg/L of aqueous ozone, over 90% removal occurred after a 16 minute treatment. Removal of dioxane was found to be driven not by ozone itself, but by radicals, suggesting that the decomposition of ozone is responsible for the generation of radical species and subsequent removal of dioxane. Ultrasound was found to increase the decomposition of ozone and appeared to be driving increased mass transfer of ozone into the aqueous phase. Modest reactor pressure appears to aid dioxane removal, but further increases in pressure did not appear to further enhance removal. An empirical model was constructed using a form similar to the Chick & Watson model for disinfection. Given inputs of initial aqueous ozone concentration, initial dioxane concentration, treatment time, and ultrasonic power, the model is able to predict effluent concentrations of dioxane with a relative root mean squared error of less than 5%. Additionally, RCT and mass balance analyses were performed, and both analysis techniques suggested that the removal of dioxane is dependent on the consumption of aqueous ozone. Spiked drinking water is representative of water that has undergone conventional treatment but requires a polishing step, and the combined ozone/ultrasound has shown promise as a polishing technology. Owing to its recalcitrance, prevalence, and mobility, dioxane represents a real and challenging groundwater contaminant, and combined ozone/ultrasound has shown promise as a groundwater treatment option. Additionally, the process is capable of dioxane removal in a pH range of 4-10. This pH independence, coupled with its ability to degrade recalcitrant contaminants, suggests that combined ozone/ultrasound holds promise as an industrial wastewater treatment option, too. The removal achieved by both ozone and combined ozone/ultrasound was an order of magnitude greater than what has been reported in previously published reports. However, a comparison of cost effectiveness relative to other advanced oxidation processes remains an area for future study. Finally, the combined ozone/ultrasound process holds promise as a drinking water treatment option in remote areas, since it requires only electricity. As a promising technology for polishing water for reuse, treating contaminated groundwater, treating industrial wastewater, and potentially improving access to safe drinking water in remote areas, combined ozone/ultrasound could aid in meeting global water demand in the future. / Civil Engineering

Modern distributed object systems pass remote parameters based on their runtime type. This design choice limits the expressiveness, readability, and maintainability of distributed applications. While a rich body of research is concerned with middleware extensibility, modern distributed object systems do not offer programming facilities to extend their remote parameter passing semantics. Thus, extending these semantics requires understanding and modifying the underlying middleware implementation. This thesis addresses these design shortcomings by presenting (i) a declarative and extensible approach to remote parameter passing that decouples parameter passing from parameter types, and (ii) a plugin-based framework, DeXteR, that enables the programmer to extend the native set of remote parameter passing semantics, without having to understand or modify the underlying middleware implementation. DeXteR treats remote parameter passing as a distributed cross-cutting concern. It uses generative and aspect-oriented techniques, enabling the implementation of different parameter passing semantics as reusable application-level plugins that work with application, system, and third-party library classes. The flexibility and expressiveness of the framework is validated by implementing several non-trivial parameter passing semantics as DeXteR plugins. The material presented in this thesis has been accepted for publication at the ACM/USENIX Middleware 2008 conference. / Master of Science

Ce travail de thèse porte sur les miels de Corse commercialisés sous l’AOC et l’AOP « Miel de Corse-Mele di Corsica » et classés en six catégories variétales : « printemps », « maquis de printemps », « miellat du maquis », « maquis d’été », « châtaigneraie » et « maquis d’automne ». Notre objectif principal était de caractériser la composition volatile des miels de Corse et de développer une approche interdisciplinaire en vue de compléter la caractérisation de ces productions par la recherche de nouveaux critères pour la qualification de l’origine botanique et/ou géographique. Les travaux ont donc consisté à croiser les données obtenues par la méthode conventionnelle basée sur les analyses polliniques, sensorielles et physico-chimiques avec celles issues de l’analyse chimique de la fraction volatile des miels.Dans une première partie, 195 miels de nectar ont été caractérisés au niveau pollinique, physico-chimique ainsi que par leurs compositions volatiles. L’analyse pollinique a permis de certifier l’origine Corse et de mettre en évidence les principales espèces nectarifères de chaque gamme variétale et/ou les associations végétales caractéristiques des miellées. L’analyse de la fraction volatile par MEPS, CPG et CPG/SM a conduit à l’identification des marqueurs chimiques des diverses variétés de miels, à savoir la 2-aminoacétophénone (« châtaigneraie ») ; le p-anisaldéhyde et le 4-n-propylanisole (« maquis de printemps ») ; l’isophorone et le 3,4,5-triméthylphénol (« maquis d’automne ») ; les isomères de lilac aldéhyde et du p-menthèn-9-al (« printemps typé clémentinier »). De plus, une étude interdisciplinaire (analyse mélissopalynologique, physico-chimique et fraction volatile) basée sur l’utilisation de traitements statistiques des données multifactorielles a été menée sur chacune des catégories variétales. Les résultats obtenus ont permis de mieux cerner l’origine botanique des miels « quasi-monofloraux » ; de proposer des hypothèses sur les autres apports nectarifères et/ou miellatifères dans les miels à taxon dominant de type sur-représenté (« châtaigneraie ») et normal (« maquis de printemps ») ; de déterminer les différentes contributions nectarifères dans les miels dont l’espèce dominante à un taxon de type sous-représenté (« printemps » et « maquis d’automne ») et dans ceux ayant une origine botanique complexe (« maquis d’été »).Dans la seconde partie de nos travaux, nous avons caractérisé la fraction volatile de 74 miels des gammes « miellat du maquis » et « miel de Corse ». L’analyse statistique de la variabilité chimique a permis de distinguer les miellats de Metcalfa par la teneur en 3-furaldéhyde. Par ailleurs, nous avons pu qualifier l’origine botanique des miels dit « génériques » (mélange « miel de miellat »/« miel de nectar »), notamment les apports significatifs de « châtaigneraie » (molécule marqueur : 2-aminoacétophénone) et/ou de « maquis de printemps » (p-anisaldéhyde et 4-n-propylanisol).Enfin, ces travaux ont permis de développer une approche innovante basée sur une approche multifactorielle (polliniques, physico-chimiques et volatils) afin de mieux qualifier la complexité des origines botaniques des miels de Corse. / This thesis was focused on the Corsican honeys under the AOC and AOP appellation “Miel de Corse-Mele di Corsica”. The Corsican honey was classified in six varietal categories: “spring”, “spring maquis”, “honeydew”, “summer maquis”, “chestnut grove” and “automne maquis”. The aim of this work was to characterize the volatile composition of Corsica honey and to develop an interdisciplinary approach to complete the characterization of Corsican honey and the qualification of the botanical and/or geographical origin. In the first part, 195 nectar honeys were characterized by melissopalynological, physico-chemical and volatile analyses. Pollen analysis allowed the certification of Corsican origin and highlights the main nectariferous species and/or characteristic plant associations of each varietal range. Thus, the volatile analysis by SPME, GC and GC/MS allowed the identification of some chemical markers of honey, namely 2-aminoacetophenone (“chestnut grove”); p-anisaldehyde and 4-n-propylanisole (“spring maquis”); isophorone and 3,4,5-trimethylphenol (“automne maquis”); isomers of lilac aldehydes and p-menth-1-en-9-al (“spring clementine”).For each honey range, an interdisciplinary study was carried out by using statistical analysis of multifactorial data (melissopalynological, physico-chemical and volatile data). These results allowed us to identify the “monofloral” honey samples; to propose some hypotheses about the nectar and/or honeydew contribution in honeys with dominant over-represented (“chestnut grove”) and normal taxon (“spring maquis”); and to determine the role of different nectariferous and/or polleniferous species in honeys with underrepresented taxon (“spring” and “autumn maquis”) and those with complex botanical origin (“summer maquis”).In the second part of our work, the volatile fraction of 74 Corsican honeydews and blend honeys has also been investigated. Statistical analysis of the volatile composition has distinguished Metcalfa honeydew by a high abundance of 3-furaldehyde. Otherwise, the other honey samples were characterized by a high abundance of 2-aminoacetopheneone (marker of “chestnut grove” honey) and/or p-anisaldehyde and 4-n-propylanisol (characteristic compounds of “spring maquis" honey). These observations could be explained by the nectar contribution of Castanea sativa and/or Erica arborea in the honeydew samples. Finally, this work has allowed us to develop an innovative approach based on multifactorial approach (pollen analysis, physic-chemical parameters, volatile composition) to obtain discriminant information for the determination of the floral origin from Corsican honeys. / U Mele di Corsica hè un pruduttu sputicu di l’isula. E prime vistighe di l’apicultura inCorsica si ritrovanu in l’Antichità più anziana ma l’arte di a bugna è di u mele vene tralasciatadopu a Sigonda guerra mundiale. Cù a mossa idintitaria di l’anni sittanta (XXu seculu),s’urganizeghjanu i prufiziunali ed ottenenu una Appillazione d’Origine Cuntrullata (AOC) inlu 1998 po una Appillazione d’Origine Prutetta (AOP) in lu 2000. Fatta fine chì a pruduzzioneoghjinca (300 à 350 tunnillate/annu), cummircializata cù a sugillata « Miel de Corse-Mele diCorsica » si spachja sigondu sei catigurie variitesche : « veranu », « machja viraninca », «milata di u machjetu », « machja d’istate », « castagnetu » è « machja auturnale ».In lu quatru di e norme naziunale (AOC) ed eurupee (AOP), u metudu cunvinziunaleda cirtificà l’origine geugrafica è butanica s’arremba à e caratteristiche pulliniche, fiscuchimicheè urganulettiche di i meli. U fine principale di sta tesi dutturale hè di caratterizà avariabbilità chimica di ste pruduzzione di modu à prupone criterii novi di qualifichera.U studiu di a frazzione vulatile di 269 campioni di meli (inclusuci e sei catigurievariitesche), hà permessu d’invinturià, pè a prima volta, a custituzione in cumposti vulatili di imeli di Corsica. I nostri travagli sò sbuccati dinò nantu à l’idintificazione di i marcadorichimichi in leia diretta cù e spicificità di i rughjoni di pruduzzione. Per quessa, un accostuinterdisciplinariu – appaghjendusi i dati di i metudi cunvinziunali cun quelli di a tippulugiavulatile- hè statu prupostu da pudè diterminà l’origine fiurale.Cusì sò stati idintificati i marcadori chimichi di parechje variità di mele, vene à dì u 2-aminoacetofenune (« castagnetu ») ; u p-anisaldeide è u 4-n-prupilanisole (« machja viraninca») ; l’isoforunu è u 3,4,5- trimetilfenule (« machja auturnale ») ; l’isomeri di lilace aldeide è diu p-menten-9-al (« veranu tippu clementinu »).Sta prima caratterizazione multifatturiale di i meli di Corsica hè propiu d’opu pèl’apicultori in lu quatru di l’evuluzione spaziu-tempurale di e pruduzzione isulane in funzionedi e cundizione di u mezu (variazione bioclimatiche, mudifica di u prucessu di e milate, rigiruapaghju).

This thesis deals with Advanced oxidation processes (AOP) and its aplication for textile wastewaters treatment and reuse. AOP is a modern technology which currently recieves increased attention due to it´s high efficiency in removing resistant and hardly-degradable pollution. Thesis consists of search and practical part. Search part is created by three chapters. First chapter describe briefly wastewater reuse. The second chapter deals with Advanced oxidation processes. AOP principle, AOP division and descriotion is included with the strong focus on the ozonation technology. The third chapter presents the textile industry and its wastewaters. The practical part of this thesis consists of two chapters. Chapter 5 describes testing of textile wastewaters decoloration by ozonation in the selected textile copany and its results. This results are used in chapter 6. Chapter 6 is the study of textile industry treatment and reuse in the selected textile company. This study contains the design of two options for wastewater treatment and reuse in the textile processes.

Software design continues to evolve from the structured programming paradigm of the 1970s and 1980s and the object-oriented programming (OOP) paradigm of the 1980s and 1990s. The functional decomposition design methodology used in these paradigms reduced the prominence of non-functional requirements, which resulted in scattered and tangled code to address non-functional elements. Aspect-oriented programming (AOP) allowed the removal of crosscutting concerns scattered throughout class code into single modules known as aspects. Aspectization resulted in increased modularity in class code, but introduced new types of problems that did not exist in OOP. One such problem was aspect interference, in which aspects meddled with the data flow or control flow of a program. Research has developed various solutions for detecting and addressing aspect interference using formal design and specification methods, and by programming techniques that specify aspect precedence. Such explicit specifications required practitioners to have a complete understanding of possible aspect interference in an AOP system under development. However, as system size increased, understanding of possible aspect interference could decrease. Therefore, practitioners needed a way to increase their understanding of possible aspect interference within a program. This study used clustering analysis to locate potential aspect interference within an aspect-oriented program under development, using k-means partitional clustering. Vector space models, using two newly defined metrics, interference potential (IP) and interference causality potential (ICP), and an existing metric, coupling on advice execution (CAE), provided input to the clustering algorithms. Resulting clusters were analyzed via an internal strategy using the R-Squared, Dunn, Davies-Bouldin, and SD indexes. The process was evaluated on both a smaller scale AOP system (AspectTetris), and a larger scale AOP system (AJHotDraw). By seeding potential interference problems into these programs and comparing results using visualizations, this study found that clustering analysis provided a viable way for detecting interference problems in aspect-oriented software. The ICP model was best at detecting interference problems, while the IP model produced results that were more sporadic. The CAE clustering models were not effective in pinpointing potential aspect interference problems. This was the first known study to use clustering analysis techniques specifically for locating aspect interference.

O processamento têxtil gera grande quantidade de despejos altamente poluidores, contendo valores elevados de carga orgânica, cor acentuada e compostos químicos tóxicos ao homem e ao meio ambiente. Os efluentes têxteis apresentam uma variação muito grande na sua composição devido aos vários tipos de corantes e produtos químicos utilizados e isto faz o seu tratamento ser um problema complexo. Devido a estas implicações, novas tecnologias têm sido buscadas para a degradação ou imobilização destes compostos em efluentes têxteis dentre os quais a combinação de processos oxidativos avançados, redutivo e separação por membranas. Os processos de separação por membranas têm sido cada vez mais aplicados para separação, purificação e concentração de constituintes industriais, principalmente pelo desenvolvimento e eficiência da técnica e redução de custos com o passar dos anos. O processo redutivo utilizando Fe0 é bastante promissor, em função do custo relativamente baixo do ferro metálico e da sua elevada efetividade na degradação de contaminantes ambientais, sendo que após a oxidação do Fe0 a íons Fe2+ e Fe3+ estes íons podem ser aproveitados em sequência nos Processos Oxidativos Avançados (POAs). Os processos oxidativos avançados são tecnologias extremamente eficientes para destruição de compostos orgânicos de difícil degradação. Podem ser consideradas tecnologias limpas, pois não há a formação de subprodutos sólidos e nem a transferência de fase dos poluentes. Os POAs são baseados na geração de radicais fortemente oxidativos, principalmente o radical hidroxila (HOo), que destroem inúmeros compostos de maneira rápida e pouco seletiva, quando comparado aos processos convencionais, conduzindo a mineralização parcial ou completa dos contaminantes. Com o objetivo de estudar o efeito destes processos na melhoria do efluente têxtil foi utilizado um efluente de uma indústria têxtil de grande porte do interior de São Paulo. Ao ser coletado, este efluente foi caracterizado e submetido à permeação por membranas de microfiltração (0,45 μm). Este tratamento possibilitou a redução de 37,7 % do COT e 40,9 % da Área Espectral (200-800 nm) em comparação com o efluente original. O efluente oriundo do tratamento com membranas foi submetido, através de planejamento de experimentos, aos processos oxidativos avançados do tipo foto-Fenton e foto-Fenton avançado (utilizando Fe0) visando à melhoria para despejo ou reúso deste efluente. Na melhor condição de reação foi possível alcançar uma redução de aproximadamente 73,0 % em COT e 93,0 % em área espectral após uma hora de reação para os dois tipos de POAs. A combinação das tecnologias de membranas e processos oxidativos avançados mostrou-se extremamente positiva quanto à melhoria da deste efluente têxtil, possibilitando a redução em torno de 83,0 % do COT e 95,0 % da área espectral. / The textile manufacturing generates large amounts of highly polluting sewage containing high levels of organic load, color and chemical compounds toxic to human beings and to the environment. This textile wastewater has a great variation in its composition due to various types of dyes and chemicals used. All these considerations make the textile wastewater treatment a complex problem. Due to these implications, new technologies have been studied for degradation or immobilization of these compounds in textile wastewater among which the combination of advanced oxidative, reductive and separation with membranes processes. The separation processes with membranes have been increasingly applied for separation, purification and concentration of industrial components, mainly development in technology and efficient cost savings over the years. The reductive process using Fe0 is very promising because of the relatively low cost of metallic iron and its high effectiveness in the degradation of environmental contaminants. After the oxidation of Fe0 to Fe2+ and Fe3+ these ions can be used in sequence in the Advanced Oxidative Process (AOPs). The advanced oxidative process technologies are extremely effective for degradation of organic compounds with difficult degradation. It can be considered as a clean technology, because there is no formation of solid subproducts, neither the phase transfer of pollutants. The AOPs are based on the generation of highly oxidative radicals, particularly hydroxyl radical (HOo), which destroys many compounds to a rapid and low selective way compared with conventional process of treatment, leading to partial or complete mineralization of contaminants. A wastewater from a large textile industry in São Paulo was used in order to study the effect of these processes in the improvement of textile wastewater quality. Firstly, the wastewater was characterized and subjected to permeation by microfiltration membrane (0.45 μm). This treatment allowed a reduction of 37.7 % of TOC and 40.9 % of spectral area (200-800 nm) compared to the original wastewater. The wastewater from the treatment with membranes was subjected, through design of experiments, the advanced oxidative processes of the type photo-Fenton and advanced photo-Fenton (using Fe0) aiming to improve the disposal or to reuse of wastewater. In the best experimental condition it was achieved a 73 % in TOC and 93 % in spectral area reduction after one hour of reaction for both types of AOPs. The membrane technologies and advanced oxidative combination process proved to be extremely positive on the textile wastewater quality improvement, resulting in a reduction of around 83 % of TOC and 95 % of spectral area.

Os efluentes corados ainda são um problema em estações de tratamento de esgoto. Os corantes normalmente apresentam estruturas complexas e difíceis de serem degradadas por processos convencionais, entrando no meio ambiente aquático e causando impacto visual, mudanças nas características físico-químicas da água, prejudicam a fotossíntese do meio e podem apresentar efeitos ecotóxicos. Para o tratamento de vários tipos de efluentes, os Processos Oxidativos Avançados (POAs) são eficientes, rápidos e promovem uma oxidação não seletiva. Os POAs podem se tornar mais eficazes com o acoplamento de outras tecnologias, como as micro-ondas. As micro-ondas não possuem energia suficiente para quebrar as ligações intermoleculares, mas quando somadas ao processo UV/H2O2 pode haver um efeito sinérgico melhorando o desempenho do POA. Neste trabalho, buscou-se a otimização do processo UV/H2O2 acoplado às micro-ondas utilizando-se uma lâmpada de descarga sem eletrodo (LDE) de Hg e Fe. Utilizou-se um planejamento experimental para estudar a degradação de uma mistura de três corantes ácidos de classes diferentes: Acid Blue 9 (C.I. 42090, triarilmetano), Acid Red 92 (C.I. 45410, xanteno) e Acid Yellow 23 (C.I. 19140, monoazo). A variável-resposta observada foi a concentração residual dos corantes medida por CLAE. As condições ótimas para o tratamento foram: concentração inicial de peróxido de hidrogênio = 125 mg L-1, pH= 6,2 e vazão = 800 mL min-1. Em 180 min de tratamento, correspondente a 45 min de irradiação alcançou-se uma degradação de 23, 20 e 98% para AB9, AR92 e AY23 respectivamente. O modelo cinético foi de pseudo 1ª ordem para o AY23, com k = (1,7 ±0,041) × 10-2 min-1 e R² = 0,990. Não foi possível determinar a cinética de degradação do AB9 e do AR92 por causa da baixa degradação alcançada (aproximadamente uma ordem de grandeza menor). A partir das análises de espectrometria de massas, observou-se um único produto de degradação: o AY23 monohidroxilado. Esse produto não apresentou ecotoxicidade para o organismo-teste L. sativa. No entanto, ele foi tóxico para o organismo D. similis, imobilizando os microcrustáceos em todas as diluições testadas. / Colored effluents are still a problem in wastewater treatment plants. Dyes usually have complex structures that are difficult to be degraded by conventional processes, thus entering into the aquatic environment and causing visual impact, changes in the water physicochemical characteristics, impairing photosynthesis, and posing ecotoxic effects. For the treatment of various types of wastewater, the Advanced Oxidation Processes (AOP) are efficient, fast and promote non-selective oxidation. AOPs can become more effective by coupling them to other technologies, such as microwaves. Microwaves do not have enough energy to break intermolecular bonds, but when coupled to the UV/H2O2 process, there may be a synergistic effect improving the AOP performance. In this study, the UV/H2O2 process coupled to microwaves, using an Hg and Fe electrodeless discharge lamp (EDL), was optimized. An experimental design was performed to study the degradation of a mixture of three acid dyes of different classes: Acid Blue 9 (C.I. 42090 , triarylmethane), Acid Red 92 (C.I. 45410, xanthene), and Acid Yellow 23 (C.I. 19140, monoazo). The observed response variable was the residual concentration of the dyes measured by HPLC. The optimum conditions for the treatment were: initial hydrogen peroxide concentration = 125 mg L- 1, pH = 6.2, and flow rate = 800 mL min-1. In 180 min of treatment, corresponding to 45 min of irradiation, it was achieved a degradation of 23, 20, and 98% for AB9, AR92, and AY23 respectively. The AY23 degradation followed a pseudo-first-order kinetic model, with k = (1.7 ±0,041) × 10-2 min-1 and R² = 0.990. It was not possible to determine the degradation kinetics of AB9 and AR92 due to the low degradation achieved (approximately one order of magnitude lower). From mass espectrometry analyses, only one degradation product was observed: monohydroxilated AY23. That product showed no ecotoxicity towards the test-organism L. sativa. However, it was toxic towards the test-organism D. similis, immobilizing the microcrustaceans in all tested dilutions.

Os efluentes corados ainda são um problema em estações de tratamento de esgoto. Os corantes normalmente apresentam estruturas complexas e difíceis de serem degradadas por processos convencionais, entrando no meio ambiente aquático e causando impacto visual, mudanças nas características físico-químicas da água, prejudicam a fotossíntese do meio e podem apresentar efeitos ecotóxicos. Para o tratamento de vários tipos de efluentes, os Processos Oxidativos Avançados (POAs) são eficientes, rápidos e promovem uma oxidação não seletiva. Os POAs podem se tornar mais eficazes com o acoplamento de outras tecnologias, como as micro-ondas. As micro-ondas não possuem energia suficiente para quebrar as ligações intermoleculares, mas quando somadas ao processo UV/H2O2 pode haver um efeito sinérgico melhorando o desempenho do POA. Neste trabalho, buscou-se a otimização do processo UV/H2O2 acoplado às micro-ondas utilizando-se uma lâmpada de descarga sem eletrodo (LDE) de Hg e Fe. Utilizou-se um planejamento experimental para estudar a degradação de uma mistura de três corantes ácidos de classes diferentes: Acid Blue 9 (C.I. 42090, triarilmetano), Acid Red 92 (C.I. 45410, xanteno) e Acid Yellow 23 (C.I. 19140, monoazo). A variável-resposta observada foi a concentração residual dos corantes medida por CLAE. As condições ótimas para o tratamento foram: concentração inicial de peróxido de hidrogênio = 125 mg L-1, pH= 6,2 e vazão = 800 mL min-1. Em 180 min de tratamento, correspondente a 45 min de irradiação alcançou-se uma degradação de 23, 20 e 98% para AB9, AR92 e AY23 respectivamente. O modelo cinético foi de pseudo 1ª ordem para o AY23, com k = (1,7 ±0,041) × 10-2 min-1 e R² = 0,990. Não foi possível determinar a cinética de degradação do AB9 e do AR92 por causa da baixa degradação alcançada (aproximadamente uma ordem de grandeza menor). A partir das análises de espectrometria de massas, observou-se um único produto de degradação: o AY23 monohidroxilado. Esse produto não apresentou ecotoxicidade para o organismo-teste L. sativa. No entanto, ele foi tóxico para o organismo D. similis, imobilizando os microcrustáceos em todas as diluições testadas. / Colored effluents are still a problem in wastewater treatment plants. Dyes usually have complex structures that are difficult to be degraded by conventional processes, thus entering into the aquatic environment and causing visual impact, changes in the water physicochemical characteristics, impairing photosynthesis, and posing ecotoxic effects. For the treatment of various types of wastewater, the Advanced Oxidation Processes (AOP) are efficient, fast and promote non-selective oxidation. AOPs can become more effective by coupling them to other technologies, such as microwaves. Microwaves do not have enough energy to break intermolecular bonds, but when coupled to the UV/H2O2 process, there may be a synergistic effect improving the AOP performance. In this study, the UV/H2O2 process coupled to microwaves, using an Hg and Fe electrodeless discharge lamp (EDL), was optimized. An experimental design was performed to study the degradation of a mixture of three acid dyes of different classes: Acid Blue 9 (C.I. 42090 , triarylmethane), Acid Red 92 (C.I. 45410, xanthene), and Acid Yellow 23 (C.I. 19140, monoazo). The observed response variable was the residual concentration of the dyes measured by HPLC. The optimum conditions for the treatment were: initial hydrogen peroxide concentration = 125 mg L- 1, pH = 6.2, and flow rate = 800 mL min-1. In 180 min of treatment, corresponding to 45 min of irradiation, it was achieved a degradation of 23, 20, and 98% for AB9, AR92, and AY23 respectively. The AY23 degradation followed a pseudo-first-order kinetic model, with k = (1.7 ±0,041) × 10-2 min-1 and R² = 0.990. It was not possible to determine the degradation kinetics of AB9 and AR92 due to the low degradation achieved (approximately one order of magnitude lower). From mass espectrometry analyses, only one degradation product was observed: monohydroxilated AY23. That product showed no ecotoxicity towards the test-organism L. sativa. However, it was toxic towards the test-organism D. similis, immobilizing the microcrustaceans in all tested dilutions.