[pt] Água produzida (AP) é uma das fases geradas a partir da separação trifásica obtida após a extração do petróleo e gás e constitui um efluente industrial. O gerenciamento do seu tratamento para descarte face a alta vazão típica e sensibilidade dos ecossistemas marinhos, é um desafio para empresas que lidam com este tipo de fluido, principalmente na extração offshore. Como este efluente tem uma composição química complexa e variável chegando em até 500 mg/L de compostos orgânicos solúveis em água (WSO), os quais não são facilmente removidos pelos tratamentos físico-químicos convencionais como coagulação e floculação, diversas alternativas de tratamento são adotadas a fim de conseguir eliminar ao máximo óleos e micropartículas de sólidos presentes. Para tal, a AP deve ser tratada antes de ser lançada ao mar ou reutilizada no processo. Contudo, nem sempre as etapas do tratamento conseguem funcionar de maneira ótima para atender a qualidade ambiental regulatória, de modo que a busca por novos processos de tratamento segue sendo de interesse geral. Neste trabalho foram testados processos de oxidação catalisada com íons Fe para incrementar a degradação de WSO, usando amostras reais de AP da Bacia de Campos (RJ, Brasil). Os melhores resultados foram obtidos nas seguintes condições de H2O2 em dose de 1x sem necessidade de catalisador (Fe2+). Nessas ocorreu uma redução de 66 por cento dos orgânicos solúveis, suficiente para manter conformidade com as exigências das normas ambientais para descarte de AP no mar. / [en] Produced water (PW) is one of the phases generated from the three-phase separation obtained after the extraction of oil and gas and constitutes an industrial effluent. The management of its treatment for disposal due to the typical high flow and sensitivity of marine ecosystems is a challenge for companies that deal with this type of fluid, especially in offshore extraction. Since this effluent has a complex and variable chemical composition reaching up to 500 mg/L of water-soluble organic compounds (WSO), which are not easily removed by conventional physicochemical treatments such as coagulation and flocculation, several treatment alternatives are adopted in order to eliminate as much as possible oils and microparticles of solids present. To reach this goal, the PW must be treated before being released into the sea or reused in the process. However, the treatment stages are not always able to function optimally to meet the regulatory environmental quality, so the studies for new treatment processes continues to be part of general interest. In this work, Fe ion-catalyzed oxidation processes were tested to increase WSO degradation, using real PW samples from the Campos Basin (RJ, Brazil). The best results were obtained under the following conditions of H2O2 at a dose of 1x without the need for catalyst (Fe2+). In these, there was a 66 percent reduction in soluble organics, sufficient to maintain compliance with the requirements of environmental standards for water discharge.

[ES] El agua se convirtió en uno de los recursos más escasos de la Tierra. Por eso es necesario desarrollar nuevas tecnologías para el tratamiento adecuado de las aguas residuales urbanas (UWW), permitiendo su reutilización. Múltiples tecnologías han demostrado ser efectivas cuando se aplican individualmente, pero a menudo no se aplican ni se integran en el tratamiento convencional de UWW, lo que resulta en la pérdida de posibles efectos sinérgicos. Por estas razones, la investigación sobre la combinación e integración de estas tecnologías es de suma importancia. Cuando se aplican de esta manera, también se conocen como Tecnologías Integradas Avanzadas. Hecho un trabajo de investigación sobre el rendimiento de una planta piloto de nanofiltración (NF) a escala piloto para UWW, seguido de la aplicación de métodos de tratamiento (químico). Los Procesos de Oxidación Avanzada (AOP), como el proceso (solar) foto-Fenton (SPF), aprovechan el ciclo catalítico del hierro (Fe2+ y Fe3+), la luz UV-vis, junto con un agente oxidante, como el peróxido de hidrógeno (H2O2), produciendo radicales hidroxilo altamente reactivos. Este proceso de foto-Fenton (solar) se aplica a un pH 3, para evitar la precipitación del hierro, o a un pH más alto mediante agentes quelantes, como el ácido etilendiamino-N, N'-disuccínico (EDDS). Los microcontaminantes (MC) usados fueron cafeína, imidacloprid, tiacloprid, carbamazepina y diclofenaco. La preconcentración es un paso esencial antes de aplicar AOP como tratamiento terciario de los efluentes de las plantas de tratamiento de aguas residuales urbanas (EDAR), ya que reduce significativamente el volumen a tratar y, por lo tanto, los costos económicos. El tratamiento de la corriente de concentrado de la NF mediante el proceso de SPF demostró ser efectivo para la eliminación de los MC mencionados anteriormente cuando se utilizó H2O2 como agente de oxidación. Por lo tanto, a una mayor degradación de los MC se adhiere una toxicidad directamente proporcionalmente menor. Las investigaciones incluyen la valorización de los efluentes EDAR mediante la recuperación de amonio, con la eliminación combinada de MC mediante NF y diferentes AOPs, con el fin de producir corrientes de permeado para la fertilización e irrigación directa de cultivos, también conocida como 'fertirrigación'. Esto incluye el proceso de SPF, pero también se combina con procesos de electrooxidación (EO). El SPF fue más efectivo al tratar las corrientes de concentrado de NF a pH circunneutro, con una concentración de MC inferior a 1 mg/L. Las corrientes de concentrado de NF altamente salinas son ideales para ser tratadas mediante procesos de EO, por sus alta conductividad, con un consumo eléctrico significativamente menor con la asistencia solar. La eficiencia de retención de MC por NF y la toxicidad después de los tratamientos con AOP también se evaluaron mediante la determinación de la fitotoxicidad del permeado. Los resultados mostraron que los permeados utilizados para los cultivos (Sorghum saccharatum, Sinapis alba, Lepidium sativum) redujeron la germinación de las semillas. Contrariamente, se observó que la irrigación con los permeados producidos generalmente promovió el desarrollo de las raíces, mientras que el desarrollo de los brotes prosperó solo cuando se usaron permeados que tenían factores de concentración inferiores al factor de concentración 2. Los estudios mostraron que los permeados deberían diluirse primero en un mínimo del 50%, para ser adecuados para la irrigación directa. El trabajo también incluyó la evaluación de una membrana de ultrafiltración (UF) cerámica foto catalítica TiO2-ZrO2 previamente desarrollada. La disminución del flujo puede revertirse cuando se irradia la membrana UF cerámica con luz en un simulador solar. La retención microbiológica de la membrana UF fue determinada utilizando una cepa bacteriana Gram negativa, Pseudomonas aeruginosa y fue capaz de retener consistentemente hasta un orden de magnitud de 1 x 104 UFC/ml. / [CA] L'aigua es va convertir en un dels productes bàsics més escassos de la Terra. Per tant, cal desenvolupar noves tecnologies, com el tractament adequat de les aigües residuals urbanes (UWW) per a la seva reutilització. Múltiples tecnologies avançades es demostren efectives quan s'apliquen únicament. Aquestes tecnologies sovint no s'apliquen ni s'integren en el tractament UWW convencional. Com a resultat, es perd possibles efectes sinèrgics. Per aquests motius, la investigació sobre la combinació i integració d'aquestes noves tecnologies és de la màxima importància. Quan s'apliquen així, aquestes tecnologies combinades també es coneixen i s'indiquen com a Tecnologies Integrades Avançades. Es va realitzar un treball de recerca sobre el rendiment d'una planta de nanofiltració (NF) a escala pilot per a la preconcentració d'UWW, seguida de l'aplicació de mètodes de tractament (químics), per tal de tractar els corrents de concentrat i permeat produïts. Els processos d'oxidació avançats (AOP), com el procés foto-Fenton (solar) (SPF), fan servir el cicle catalític del ferro (Fe2+ i Fe3+), la llum UV-vis, juntament amb un agent oxidant, com el peròxid d'hidrogen (H2O2), produint radicals hidroxil altament reactius i no selectius. Aquest procés SPF s'aplica a pH3, per tal d'evitar la precipitació del ferro, o a pH circumneutral aplicant agents quelants com l'àcid etilendiamina-N, N¿-disuccinic (EDDS). La preconcentració és un pas essencial abans d'aplicar els AOP com a tractament terciari d'efluents d'EDAR, ja que redueix significativament el volum a tractar i, per tant, els costos globals. El tractament del corrent de concentrat del NF mitjançant el procés SPF va demostrar ser eficaç per a l'eliminació de diferents microcontaminants (MC) quan s'utilitzava H2O2 com a agent d'oxidació. Per al qual una degradació de MC més alta s'adhereix a una toxicitat menor directament proporcional. Els seleccionats (MC) van ser cafeïna, imidacloprid, tiacloprid, carbamazepina i diclofenac. Els treballs de recerca posteriors van tractar la valorització dels efluents d'EDAR mitjançant la recuperació d'amoni, amb l'eliminació combinada de MC per NF i diferents AOP avançats, per tal de produir corrents permeats per a la fertilització directa dels cultius i el reg, també anomenats "fertirrigació". Inclou SPF, però també combinat amb processos d'electrooxidació (EO). El SPF va ser més eficaç quan es tractaven corrents de concentrat de NF a pH circumneutral, a una concentració de MC inferior a 1 mg/L, per obtenir una degradació ràpida de MC. Els corrents concentrats de concentrat NF altament salins són ideals per ser tractats mitjançant processos EO, alhora que posseeixen una alta conductivitat, i un menor consum elèctric significatiu per assistència solar. També es va avaluar l'eficiència de retenció de MC per NF i la toxicitat després dels tractaments amb AOP determinant la fitotoxicitat del permeat. Els resultats van mostrar que els permeats podrien reduir la germinació de llavors si s'utilitzaven per a cultius (Sorghum saccharatum, Sinapis alba, Lepidium sativum). Al contrari d'això, es va demostrar que el reg amb els permeats produïts afavoria generalment el desenvolupament de les arrels, mentre que el desenvolupament dels brots només va prosperar quan s'utilitzaven permeats que tenien factors de concentració inferiors a 2. Els estudis de toxicitat van mostrar que els corrents de permeat s'havien de diluir primer amb un mínim del 50% aigua dolça. El treball de recerca realitzat també va incloure l'avaluació d'una membrana d'ultrafiltració ceràmica (UF) fotocatalítica TiO2-ZrO2 desenvolupada prèviament. La disminució del flux es pot revertir quan la membrana fotocatalítica UF va ser irradiada per llum en un simulador solar. La retenció microbiològica de la membrana UF es va determinar mitjançant el desplegament d'una soca bacteriana gramnegativa, Pseudomonas aeruginosa, ser capaç de retenir constantment fins a un ordre de magnitud d'1 x 104 CFU/ml. / [EN] Water turned to be one of Earths scarcest commodities. Therefore, novel technologies need to be developed, as appropriate treatment of produced urban wastewaters (UWWs) for its reuse as irrigation waters or aquifer recharge. Multiple advanced technologies are proven effective when applied solely. These technologies are often not applied or integrated into conventional UWW treatment. Resulting in missing out on potential synergetic effects. For these reasons that research into the combining and integration of these novel technologies is of the utmost importance. When thus applied, these combined technologies are also known and indicated as Advanced Integrated Technologies. Research work was conducted on the performance of a pilot scale nanofiltration (NF) plant for UWW pre-concentration, followed by the application of (chemical) treatment methods, in order to treat the produced concentrate and permeate streams. Advanced Oxidation Processes (AOPs), such as the (solar) photo-Fenton process make use of the catalytic cycle of iron (Fe2+ and Fe3+), UV-vis light, along with an oxidizing agent, such as hydrogen peroxide (H2O2), producing highly reactive and non-selective hydroxyl radicals (¿OH). This (solar) photo-Fenton process is applied at acidic pH3, in order to prevent iron precipitation, or at circumneutral pH by applying chelating agents such as Ethylenediamine-N, N¿-disuccinic acid (EDDS). Preconcentration is an essential step before applying AOPs as tertiary treatment of UWWTP effluents, as it significantly lowers the to be treated volume, and therefore the overall costs. Treating the concentrate stream from the NF by the solar photo-Fenton process showed to be effective for the removal of different microcontaminants (MCs) when H2O2 was used as an oxidation agent. Opposite to that, the application of persulfate and its derived radicals showed lower degradation of the selected MC. For which a higher MC degradation is adhered to a directly proportional lower toxicity. Selected (MCs) were caffeine, imidacloprid, thiacloprid, carbamazepine, and diclofenac. Further research work covered UWWTP effluent valorization by the recovery of ammonium, with combined MC elimination by NF and different advanced AOPs, in order to produce permeate streams for direct crop fertilization and irrigation, also called 'fertigation'. Including solar photo-Fenton, but also combined with electrooxidation (EO) processes. Solar photo-Fenton was most effective when treating NF concentrate streams at circumneutral pH, at MC concentration lower than 1 mg/L, to obtain rapid MC degradation. High saline and concentrated NF concentrate streams are ideal to be treated by EO processes, while possessing high conductivity. Obtaining significant lower electric consumption by solar assistance. MC retention efficiency by NF and toxicity after AOP treatments was also assessed by determining the permeate phytotoxicity. Results showed that permeates could lower seed germination if they would be used for crops (Sorghum saccharatum, Sinapis alba and Lepidium sativum). Contrary to that, it was showed that irrigation with the produced permeates generally promoted root development, while shoot development only thrived when using permeates which had concentration factors lower than 2. Toxicity studies showed that permeate streams should first be diluted with a minimum of 50% fresh water, in order to be suitable for direct crop irrigation in agriculture. Conducted research work also included the assessment of a priorly developed (collaboration with an PhD within MSCA AQUAlity) photocatalytic TiO2-ZrO2 ceramic ultrafiltration (UF) membrane. Flux decline can be reversed when the photocatalytic UF membrane was irradiated by light in a solar simulator. Microbiological retention of the UF membrane was determined by deploying a Gram-negative bacterial strain, Pseudomonas aeruginosa (P. Aeruginosa). It was able to consistently retain till an order of magnitude of 1x10^4 CFU/ml. / This PhD Thesis has received funding from the European Union’s Horizon 2020 research and innovation program, the AQUAlity project, under the Marie SkłodowskaCurie grant agreement No 765860. Performing research work at CIEMAT – Plataforma Solar de Almería. / Deemter, RD. (2024). Application of Advanced Integrated Technologies (Membrane and Photo-Oxidation Processes) for the Removal of CECs contained in Urban Wastewater [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203099

Soils contaminated by hydrophobic organic pollutants like polycyclic aromatic hydrocarbons (PAHs) are a common concern since they are extremely difficult to remove and their potential toxicological impacts are significant. As an alternative to traditional thermal or physical treatments, soil washing and soil flushing processes appear to be conceivable and efficient approaches, especially for higher level of pollution. However, the treatment of highly loaded soil washing/flushing solutions is another challenge to overcome. In that way, a new integrated approach is suggested: soil washing/flushing processes combined to an electrochemical advanced oxidation process (EAOP) in a combination with a recirculation loop (to save extracting agents) and/or a biological post-treatment step (to minimize energy cost).Extraction efficiency of the extracting agent like hydroxypropyl-beta-cyclodextrin (HPCD) is compared to the traditional non-ionic surfactant Tween 80 in synthetic and real soil washing solutions. A new simple fluorescent sensitive and selective quantification method is developed to monitor Tween 80 oxidation. Two EAOPs were compared: electro-Fenton (EF) and anodic oxidation (AO). Platinum (Pt) (in EF process) and boron doped diamond (BDD) (in both treatment) anodes are the respective electrodes employed to recycle effluents and to consider a biological post-treatment, respectively. Regarding the extracting agent recovery, the biodegradability evolution of effluent and the energy consumption (in kWh (kgTOC)-1) during EAOP, HPCD is more advantageous than Tween 80. However, in terms of extraction efficiency, costs of extracting agents and impact on soil respirometry, Tween 80 is much more efficient. By considering all these advantages and drawbacks, Tween 80 could still appear to be the best option

La première partie de ce travail de thèse s'inscrit dans le cadre de la dépollution des eaux contaminées par les polluants organiques persistants et plus en particulier par les résidus pharmaceutiques. Des techniques alternatives telles que les procédés d'oxydation avancée (POA) qui utilisent comme agent oxydant les radicaux OH, ont été appliquées à la dégradation et/ou à la minéralisation d'un polluant médicamenteux, l'Ibuprofène, en milieu aqueux. Il a été choisi comme molécule modèle en raison de son grand volume de prescription et de sa présence prouvée dans les effluents des stations d'épuration et dans les eaux naturelles. Notre étude a consisté notamment à la recherche d'optimisation des paramètres opératoires tels que la concentration de H2O2 et de Fe2+ ainsi que leur rapport pour générer les radicaux hydroxyles par le procédé photo-Fenton, et la concentration (et nature) de l'électrolyte de support et l'intensité du courant appliqué pour les procédés électrochimiques électro-Fenton et oxydation anodique. En outre, l'évolution de la toxicité de cette molécule a été suivie par la méthode Microtox au cours du traitement par le procédé d'oxydation anodique. La cinétique d'oxydation et de minéralisation de l'ibuprofène a été étudiée. La constante de réaction d'oxydation de l'ibuprofène avec les radicaux hydroxyles a été déterminée par la méthode de cinétique de compétition comme 3,84 109 M-1 s-1. Nos résultats montrent que l'application de ces procédés est efficace pour éliminer ce produit pharmaceutique de l'eau. On atteint la dégradation complète du polluant, et une minéralisation quasi-totale de la matière organique. La deuxième partie englobe une étude expérimentale sur les propriétés physiques (à différentes échelles) et le comportement mécanique des Basaltes. On a étudié le comportement mécanique et les modes de rupture d'un basalte poreux des Açores. Les résultats sont obtenus lors d'essais en contrainte triaxiale, en conditions totalement drainées et à température ambiante. Ce basalte présente deux modes de déformation. À faible pression de confinement, les échantillons présentent un comportement mécanique fragile et une déformation localisée (bande de cisaillement). Pour des pressions de confinement plus élevées, le basalte présente un comportement ductile et des compactions localisées (bandes de compaction). Les données mécaniques ont permis de déterminer l'enveloppe complète du domaine élastique. La quantification des propriétés physiques de deux types de basaltes des Galápagos a été effectuée à pression et température ambiante. Dans le but d'étudier l'effet de la fissuration sur les propriétés physiques, les échantillons on été soumis à des traitements thermiques. Enfin, pour étudier la réponse de la roche aux conditions de pression auxquelles elle est soumise en profondeur, des mesures de vitesses des ondes sous pression ont été acquises. Les résultats obtenus et l'utilisation de modèles théoriques ont permis de quantifier la densité de fissures initiales et de celles induites par les traitements thermiques, ainsi que le facteur de forme de celles-ci. L'ensemble des propriétés physiques ont permis de mieux comprendre le rôle du réseau poreux de la roche sur les propriétés physiques. Cette étude de laboratoire a été nécessaire pour l'interprétation des données recueillies in situ par sismique réfraction / The first part of this thesis is focused on the remediation of waters contaminated with persistent organic pollutants, in particular pharmaceutical products. Alternative technologies such as the advanced oxidation processes (AOPs), which based on the generation of hydroxyl radicals OH, were applied to the degradation and/or mineralization of a pollutant drug, ibuprofen, in aqueous medium. We chose this pollutant as a model molecule to study due to its large volume of prescription and to its proved presence in the effluents of sewage plants and natural waters. The main objective of this work was the optimization of operational parameters of the applied AOPs. The concentration of H2O2 and Fe2+ reagents ratio to generate hydroxyl radicals for photo-Fenton process, and supporting electrolyte concentration (and the nature) and the applied current for both electro-Fenton and anodic oxidation processes. The oxidation and mineralization kinetics of the ibuprofen were studied and the absolute rate constant for the oxidative degradation of ibuprofen was determined by the competition kinetic method, being 3,84 109 M-1s-1. Toxicity tests of the drug solutions during the anodic oxidation process were carried out by the Microtox method. Our results show that these methods are effective for the degradation of this pharmaceutical product from water. Ibuprofen was completely degraded and the organic matter was almost completely mineralized after the application of these processes. The second part of the thesis includes an experimental study of the physical properties (at different scales) and the mechanical behavior of basaltic rocks. We studied the mechanical behavior and the failure modes of a porous basalt from Azores. Results were acquired under triaxial compression experiments on water saturated samples at room temperature. This basalt presented two modes of deformation. At low confining pressure, the samples exhibited a brittle mechanical behavior and a localized deformation (shear band). For higher confining pressure, this basalt showed a ductile behavior and localized compactions (compaction bands). The mechanical data allows us to plot the full yield surface for the porous basalt. The quantification of the physical properties of two types of basalts from the Galapagos was performed at room temperature and pressure. In order to study the effect of cracking on the physical properties of these basalts, samples were subjected to thermal treatments to induce thermal crack damage. Finally for the less porous basalt, measures of wave velocities under the pressure at which it is subjected in depth were acquired. The obtained results and the following application of models with them allow quantifying the density of initial cracks and of those induced by thermal treatments, as well as quantifying the aspect ratio of cracks. The studied physical properties led to better understand the role of the pore network of the rock in these physical properties. This laboratory study was necessary for the interpretation of data collected in situ by seismic refraction method

Ce travail est consacré à l’étude d’un procédé d’oxydation avancée (POA) basé sur la génération de radicaux sulfates (SO4•-) pour l’élimination de substances pharmaceutiques dans le cadre du traitement d’effluents urbains. Quatre substances pharmaceutiques azotées (carbamazépine, diclofénac, sulfaméthoxazole et ciprofloxacine) appartenant à des familles thérapeutiques différentes ont été choisies en tant que contaminants modèles. L’évaluation de la performance cinétique des procédés basés sur la génération de HO• (H2O2/Fe(II) et UV-C/H2O2) et de SO4•- (HSO5-/Co2+, UV-C/S2O82- et UV-C/HSO5-) a été conduite dans des effluents de stations d'épuration traités biologiquement. La comparaison des procédés non photochimiques et photochimiques a été conduite dans les mêmes conditions optimales et montre que les procédés générant des SO4•- sont moins inhibés par la matrice environnementale que les procédés produisant HO•. La réaction de transfert électronique est mise en évidence par l’identification de produits de transformation des contaminants d’étude par chromatographie liquide couplée à un spectromètre de masse à haute résolution. Le début d’oxydation démarre par un transfert d’un électron sur les groupements azotés générant ainsi un radical cation qui réagit avec l’eau ou l’O2. La dégradation du sulfaméthoxazole est le cas le plus évident grâce à sa fonction amine primaire (aniline) qui se transforme en fonction nitro. On peut par conséquent envisager des nouvelles stratégies de traitement des eaux usées urbaines par la génération de SO4•-. / This work is devoted to the study of an alternative advanced oxidation process (AOP) generating sulfate radical (SO4•-) for the removal of pharmaceuticals in municipal wastewater effluents. Four nitrogen containing pharmaceuticals (carbamazepine, diclofenac, sulfamethoxazole and ciprofloxacin) belonging to different therapeutic classes were chosen as model contaminants. The evaluation of the kinetic performance of processes based on the generation of HO• (H2O2/Fe(II) and UV-C/H2O2 ) and SO4•- (HSO5-/Co2+, UV-C/S2O82- and UV-C/HSO5- ) was conducted in biologically treated effluent. Comparison of photochemical and non- photochemical processes performed under the same optimal conditions showed that the processes generating SO4•- are less inhibited by the environmental matrix than processes producing HO•. This electron transfer reaction is demonstrated by the identification of transformation products using liquid chromatography coupled to high resolution mass spectrometer. Oxidation of parent compounds starts by an electron transfer reaction on the nitrogen groups thereby generating a cation radical which further reacts with water or O2. The sulfamethoxazole degradation pathway gives more insights into this mechanism due to the primary amine moiety (aniline) which is converted into nitro function. This treatment system can be regarded as a new strategy for the treatment of urban wastewater contaminated by pharmaceutical residues through the generation of SO4•-.

O efluente lácteo é caracterizado pelo elevado teor de matéria orgânica. Os principais impactos ambientais causados pelas indústrias de laticínios estão relacionados ao lançamento dos efluentes líquidos, geralmente com ineficiente controle ou tratamento, sendo de fundamental importância a implementação de técnicas de tratamento eficazes e de baixo custo. Dentro desta proposta, os chamados Processos Oxidativos Avançados (POAs) são tecnologias eficientes para a oxidação (parcial ou total) de compostos orgânicos de difícil degradação. O presente trabalho de pesquisa objetivou a avaliação da potencialidade da ozonização catalítica, para a redução da carga orgânica do efluente proveniente da indústria de laticínio Cia de Alimentos Glória da cidade de Guaratinguetá, oriundos do processamento de beneficiamento de leite, utilizando-se Fe2+ como catalisador em processo semi-batelada com reciclo. A caracterização do efluente lácteo in natura foi realizada empregando-se métodos estabelecidos e otimizados de alguns parâmetros elencados nas legislações ambientais, destacando-se: DQO, COT, DBO5, Nitrogênio (orgânico e amoniacal), Fósforo total, Ferro, Sólidos (ST, STF, STV), surfactantes aniônicos, óleos e graxas e elementos metálicos. Através de planejamento fatorial fracionado 24-1, determinaram-se as melhores condições entre as variáveis potência do ozonizador, vazão de O2, concentração de Fe2+ e pH para a etapa de tratamento com POA, tendo como fator de resposta a redução da DQO e COT. Avaliou-se também uma nova configuração de reator em função de uma espuma formada durante o processo de tratamento. Os resultados obtidos para o conjunto de experimentos mostraram-se promissores, sendo que a redução média de COT com 63,95 % e de DQO com 70,50 % para o ensaio com as variáveis da reação otimizada, com o custo no valor de R$ 0,056 / L de efluente. Após o processo de ozonização catalítica, a amostra do melhor experimento: pH 4,0, concentração de Fe2+ 1,0 g L-1, potência 86 W, vazão de O2 0,5 L min-1, tendo como vazão mássica de O3 3,10 mg min-1, foi tratada por um processo biológico - Sistema Lodo Ativado (SLA), a fim de verificar a eficiência de degradação da matéria orgânica do efluente estudado através do sistema conjugado (POA - SLA). Os resultados para o tratamento híbrido apresentou percentuais de reduções para COT de 82,95 %, DQO de 95,60 % e DBO de 93,09 %. / Dairy effluent is characterized by the high content of organic material. The major environmental impacts caused by dairy industries are related to the release of liquid effluents, generally with an inefficient control or treatment, which makes it essential to implement effective treatment techniques, at a low cost. Within this proposal, Advanced Oxidation Processes (AOPs) are efficient technologies for oxidation (partial or total) of organic compounds of difficult degradation. This research study aimed at assessing the potential of catalytic ozonation for reduction of the effluent organic load from the dairy industry Cia de Alimentos Glória located in the city of Guaratinguetá, State of São Paulo, Brazil, derived from milk processing, using Fe2+ as catalyst in a semi-batch process with recycle. The characterization of milky effluent in natura was performed by using established and optimized methods of some parameters listed in environmental legislation, among them: COD, TOC, BOD5, Nitrogen (organic and ammoniacal), total Phosphorus, Iron, Solids (TS, FTS, VTS), anionic surfactants, oils and greases and metallic elements. Through fractional factorial design 24-1, the best conditions among the power variables of the power ozonator, O2 flow, Fe2+ concentration and pH were determined for the treatment stage with AOP, with a response factor of COD and TOC reduction. A new configuration of reactor was also assessed due to the presence of foam during the treatment process. The obtained results for the set of experiments were found to be promising, with an average reduction of TOC of 63.95 % and of 70.50 % for COD for the test with optimized reaction variables, with a cost of U$$ 0.02 / L of effluent. After the catalytic ozonation process, the sample of the best experiment was: pH 4.0, concentration of Fe2+ 1.0 g L-1, power of 86 W, flow of O2 0.5 L min-1, with mass flow of O3 3.10 mg min-1, was treated by a biological process in order to verify to verify the efficiency of degradation of the organic matter of the effluent studied through the conjugated (AOP - AS) system.The results for the hybrid treatment showed percentages of reductions for TOC of 82.95 %, COD of 95.60 % and BOD5 of 93.09 %.

A indústria farmacêutica acarreta a geração de uma quantidade significante de resíduos potencialmente poluidores. Ao serem lançados em corpos d\'água, os efluentes das indústrias farmacêuticas provocam desequilíbrio no ambiente, por transportarem compostos de difícil degradação. A ocorrência desses resíduos no ambiente pode favorecer a resistência de microrganismos frente a esses fármacos, além de causar problemas de ordem toxicológica a determinados organismos vivos. No intuito de minimizar os impactos causados pelos despejos dos efluentes desta atividade industrial, torna-se necessário estudar tratamentos alternativos para degradação de tais resíduos. Esta pesquisa teve como proposta avaliar um Processo Oxidativo Avançado: Ozonição Catalítica Homogênea em presença de íons Fe2+ como técnica para tratamento de efluente veterinário, para tanto foram estudados três diferentes reatores em sistema contínuo. Na primeira etapa do estudo, foi definido o modelo de reator mais adequado para o tratamento desse efluente farmacêutico veterinário. Na segunda etapa do estudo, utilizou-se um planejamento fatorial fracionado 24-1 para otimizar as variáveis do processo: pH, concentração de Fe2+ g/L, potência do ozonizador (vazão mássica de O3) e vazão de saída do efluente do reator. A eficiência do tratamento foi avaliada por meio da redução de Carbono Orgânico Total (COT) (%). Este estudo mostrou que a condição experimental na qual se observou a maior porcentagem de redução de COT (46,14%) ocorreu quando se combinou pH 4,0, [Fe2+] de 0,5 g/L, vazão de saída do reator de 1,23 L/h e potência do ozonizador de 56W. A avaliação estatística desse planejamento apontou para uma nova configuração experimental na qual se obteve 55,24% de redução de COT, degradação do ativo Fenbendazol de 71,24% e degradação do ativo Triclabendazol de 95,68%. Essa nova configuração combinou pH 4,0, [Fe2+] de 0,1g/L, vazão de saída do reator de 1,85 L/h e potência de 56W. / The pharmaceutical industry generates a significant amount of potentially polluting waste. When released into stream, the pharmaceutical effluents cause imbalance in the environment, transporting compounds are difficult to degrade. The occurrence of these residues in the environment can improve the microbial resistance of these drugs and cause toxicological implication of certain organisms. In order to minimize the impacts caused by discharges of effluents of this industrial activity, it is necessary to study alternative treatments for degradation of the waste. The purpose of this work was to evaluate proposed system using continuous reactors as one treatment technique Advanced Oxidative Process: Catalytic Homogeneous Ozonization with Fe2+. In the first stage of the study, the reactor model more suitable for treatment of this veterinary pharmaceutical effluent. In the second stage of the study, used a design factorial 24-1to optimize the variables of the process: pH, concentration of Fe2+ g/L, ozoniser power and output flow reactor. The efficiency of the treatment was evaluated by the reduction of Total Organic Carbon rate (TOC) (%). This study showed that the experimental condition in which it was observed the highest percentage of TOC reduction (46.14%) occurred when combined pH 4.0, [Fe 2 +] 0.5 g / L, the output flow reactor 1.23 L / h and ozoniser power of 56W. The statistical evaluation of this planning pointed to a new experimental setup in which we obtained 55.24% reduction of TOC, degradation of drug Fenbendazole 71.24% and degradation of 95.68% drug Triclabendazole. This new configuration combined pH 4.0, [Fe 2 +] of 0.1 g / L, output flow reactor of 1.85 L / h and ozoniser power of 56W.

Bisphenol A (BPA) is widely used in the production of plastics, epoxy resins and polycarbonates. It is a toxic, endocrine disruptor compound. Different studies have shown the presence of BPA in several environmental systems, classifying it as a worldwide persistent pollutant which may act synergistically with other pollutants. In this context, advanced oxidation processes (AOP) have received great attention due to their ability to degrade pollutants with such characteristics, through their transformation into less hazardous compounds or even their mineralization. Although there are investigations on the use of AOPs for BPA degradation, systematic studies on the effects of process variables, coupled with the statistical interpretation of the results are virtually non-existent. Furthermore, to the best of our knowledge, a rigorous kinetic model has not yet been proposed for the degradation of this pollutant by the H2O2/UV process. The objective of this work was to evaluate BPA degradation by the H2O2/UV process, investigating the effects of the initial H2O2 concentration and the specific rate of photons emission (EP,0) by means of a Doehlert experimental design, combined with the response surface methodology. The experiments were performed in a photochemical tubular reactor equipped with a 254-nm UV lamp, for [H2O2]0 and EP,0 in the ranges 1.6-9.6 mmol L-1 and 0.87 × 1018-3.6 × 1018 photons L-1 s-1, respectively. Total BPA degradation was achieved after 60 min of irradiation in all experiments. The best conditions were [H2O2]0 = 7.6 mmol L-1 and EP,0 = 3.6 × 1018 photons L-1 s-1, for which the best performance was obtained regarding the BPA degradation rate, BPA degradation after 15 min, and the second highest TOC removal after 180 min. However, in most experiments less than 75% TOC removal was observed, with 95% mineralization obtained only for the superior [H2O2]0 and EP,0. A mathematical model was developed, considering the reactor characteristics and the radiation field, based on the line source with parallel emission (LSPP) approach, in combination with the radiative transfer equation (RTE), mass balances, and a detailed kinetic model of the H2O2/UV process. The steady-state approximation was applied for all radical species. In the estimation of unknown kinetic constants, the non-linear least squares method was employed. The model was able to satisfactorily fit experimental BPA and H2O2 concentrations as a function of time. This work shows that the H2O2/UV process is a good alternative for BPA removal from aqueous streams, with total degradation of the target compound and adequate percent mineralization under optimal operating conditions. Such conditions may serve as first guidelines for pilot-plant and industrial processes operation. In addition, simulations using the proposed kinetic model may provide useful information for the design and scale-up of pre- or post-treatment of effluents containing this pollutant. / O bisfenol A (BPA) é amplamente utilizado na fabricação de plásticos, resinas epóxi e policarbonatos. Trata-se de um composto tóxico e um desregulador endócrino. Diferentes estudos evidenciam a presença do BPA em diversos compartimentos ambientais em todo planeta, identificando-o como um poluente persistente e resistente à degradação biológica, que apresenta efeitos sinergéticos com outros poluentes. Nesse contexto, os processos oxidativos avançados (POA) têm recebido atenção devido a sua capacidade em degradar poluentes com tais características, transformando-os em compostos menos perigosos ou até mesmo mineralizando-os totalmente. Apesar de haver trabalhos na literatura acerca da utilização de POA para degradação de BPA, estudos sistemáticos dos efeitos de variáveis de processo junto com a interpretação estatística dos resultados são virtualmente inexistentes. Além disso, até onde se sabe um modelo cinético rigoroso ainda não foi proposto para a degradação desse poluente por meio do processo H2O2/UV. Este trabalho teve por objetivo avaliar a degradação do BPA pelo processo H2O2/UV, investigando os efeitos da concentração inicial de H2O2 e da taxa específica de emissão de fótons (EP,0) por meio de um projeto experimental Doehlert, combinado com a análise de superfície de resposta. Os experimentos foram realizados em um reator tubular fotoquímico equipado com uma lâmpada UV de 254 nm, para [H2O2]0 e EP,0 entre 1,6-9,6 mmol L-1 e 0,87 × 1018 - 3,6 × 1018 fótons L-1 s-1, respectivamente. Todos os experimentos sob H2O2/UV resultaram em total degradação do BPA após 60 min de irradiação. Nesse caso, as melhores condições foram [H2O2]0 = 7,6 mmol L-1 e EP,0 = 3,6 × 1018 fótons L-1 s-1, para as quais se obteve o melhor desempenho quanto à taxa de degradação de BPA e à remoção após 15 min, e a segunda maior remoção de COT após 180 min. Entretanto, na maioria dos experimentos menos de 75% de remoção de COT foram observados, com 95% de mineralização obtida apenas para os maiores [H2O2]0 e EP,0. Elaborou-se um modelo matemático que considera as características do reator utilizado e o campo de radiação, baseado no modelo de fonte linear de emissão em planos paralelos (LSPP), combinado à equação de transferência radiativa (RTE), aos balanços materiais e a um modelo cinético detalhado do processo H2O2/UV. Foi empregada a aproximação de estado estacionário para todas as espécies radicalares. Na estimativa das constantes cinéticas desconhecidas, utilizou-se o método de mínimos quadrados não linear. Esse modelo foi capaz de ajustar satisfatoriamente as concentrações experimentais de BPA e de H2O2 em função do tempo. Este trabalho mostra que o processo H2O2/UV constitui uma alternativa conveniente para a degradação de BPA em matrizes aquosas, com total degradação do composto alvo e porcentagem de mineralização adequada nas condições ótimas de operação. Tais condições podem servir como diretrizes iniciais de processamento em escalas piloto e industrial. Por sua vez, simulações empregando o modelo matemático proposto permitem gerar informações úteis para projeto e aumento de escala de processos de pré- ou pós-tratamento de efluentes contendo esse poluente.

Neste trabalho, foram sintetizados complexos de cobre e ferro, com ligantes imínicos, obtidos a partir de 2-acetilpiridina e 2-(2-aminoetilpiridina) (apyepy), ou 2-acetilpiridina e 2-(aminometil)benzimidazol (apyambi), e com ligantes comerciais (ácido nitrilotriacético ou picolínico), capazes de catalisar a oxidação de poluentes, como benzeno, tolueno, etilbenzeno e xilenos (BTEX). Foi utilizado o tolueno como composto-modelo destes poluentes, que foi degradado com o uso de peróxido de hidrogênio, persulfato de sódio, ácido peracético ou peróxidos de metais alcalinos como agentes oxidantes. Os ligantes imínicos foram obtidos a partir de precursores carbonílicos e amínicos adequados, através de reações de condensação, e os correspondentes complexos metálicos de cobre(II), ferro(II) ou ferro(III) foram isolados utilizando métodos usuais de nosso laboratório. A caracterização dos compostos foi feita através de diversas técnicas analíticas e espectroscópicas: UV/Vis, infravermelho (IV) e de ressonância paramagnética eletrônica (EPR). Posteriormente, foi feita a inserção desses complexos de ferro e de cobre sintetizados em matrizes inorgânicas de niobatos e a verificação de sua reatividade em comparação com as mesmas espécies em solução. Monitorou-se a degradação do tolueno pelo peróxido de hidrogênio por cromatografia gasosa e os resultados obtidos indicaram boa atividade catalítica dos complexos, tanto em solução como inseridos em matrizes de niobato. Em solução, os complexos imínicos foram mais ativos que os de ligantes comerciais. Os compostos de ferro com ambos os ligantes imínicos mostraram-se melhores catalisadores que os correspondentes de cobre e um dos ligantes testados foi o mais eficiente (apyepy) com ambos os metais. A inserção em niobatos, aparentemente, preserva o catalisador e mantém sua atividade por mais tempo, mostrando que a inserção em niobatos beneficia o processo / In this work, iron and copper complexes were synthesized, with imine ligands obtained from 2-acetylpyridine and 2-(2-aminethylpiridine) (apyepy), or 2- acetylpyridine and 2- (aminomethyl)benzimidazole (apyambi) and commercial ligands (nitriletriacetic and picolinic acids) that are able to catalyze the oxidation of pollutant compounds as benzene, , ethylbenzene and xilenes (BTEX). Toluene was used as model compound of those pollutants, and its degradation was verified by using hydrogen peroxide, alkaline peroxide, sodium persulfate, or peracetic acid as oxidant agent. The imine ligands were obtained from adequate carbonyl and amine precursors, in condensation reactions, and the corresponding copper(II), iron(II) and iron(III) complexes were isolated by usual methods developed in our laboratory. Their characterization was carried out by analytical and spectroscopic techniques (UV/Vis, IR and EPR). Those complexes were then inserted in inorganic matrices (niobates) e its reactivity were compared to that of the analogous species in solution. Toluene degradation by hydrogen peroxide was monitored by gas chromatography, and the results showed good catalytic activity of all the complexes, both in solution and inserted into niobate matrices. In solution, the imine complexes were more efficient than the species with commercial ligands. The iron compounds with both imine ligands acted as better catalysts than the corresponding copper species, and for both metals those with the ligand apyepy were the most efficient in both cases. The insertion in niobates apparently preserves the catalyst and maintains its activity for longer, attesting that the insertion ameliorated the process.

Durante anos, o lixo da cidade de Guaratinguetá foi aterrado e o seu produto recalcitrante não passou por nenhum tratamento físico ou mesmo químico, percolando diretamente sob o aterro. Mesmo tendo sido desativado e transformado em Parque Ecológico, o material depositado no local ao longo dos anos, continuará a ser decomposto por microrganismos e continuará a ser produzido o lixiviado como fonte de poluição ambiental. Inicialmente, fez-se a caracterização do chorume \"in natura\", demonstrando-se como fonte de matéria orgânica recalcitrante, com massa molar característica de macromoléculas (5,58 kDa e polidispersidade de 1,16), DBO não determinável pela recalcitrância molecular e/ou pela ação tóxica e DQO característica de lixiviado estabilizado (1.013 mg L-1). A fração inorgânica total, dada pela quantidade de sólidos fixos, foi de 3.670 mg L-1, valor esse 3,6 vezes maior que a fração orgânica. O estudo de tratamento do chorume, por ozonização catalítica homogênea foi desenvolvido, principalmente, pelo uso seqüencial de dois arranjos ortogonais de Taguchi, sendo o primeiro, matriz L16, para estudo exploratório dos fatores mais importantes na redução percentual da DQO. Os fatores estudados foram vazão de ozônio, concentração dos íons Fe2+, Fe3+, Zn2+, Mn2+, Ni2+ e Cr3+, pH do meio reacional e presença/ausência de fonte de radiação UV (254 nm). Dentre os metais de transição, os íons Fe2+ e Fe3+ demonstraram-se como mais viáveis como catalisadores na geração de radicais livres hidroxilas devido à sua significância estatística (p = 0,005), e por terem maior tolerância ao descarte no meio ambiente (menor toxicidade) frente aos demais íons. Com a utilização do arranjo ortogonal L8 de Taguchi, foi possível atingir degradação máxima de DQO da ordem de 50 %. A melhor configuração dos fatores, visando aumentar o percentual de redução da DQO foi: vazão de ozônio igual a 5 L h-1 (589,9 mg h-1 O3), concentração de íon de íon ferroso igual a 10 mg L-1, concentração de íon férrico igual a 5 mg L-1 e pH 5. / During many years, the garbage of Guaratinguetá city was landfilled and its recalcitrant product was not submitted to any physical or chemical treatment, leaching directly through the area. After deactivating and transforming the landfill into an Ecological Park, the material deposited in the place by the past years, will continue being decomposed by microorganisms and will continue producing the leached one as a mean of environment pollution. Initially, the leachate \"in natura\" was characterized, demonstrating itself as a source of recalcitrant organic substance with a higher molecular size characteristic of 5,58 kDa and polidispersity of 1,16 and stabilized effluent (not determinable DBO due to molecular recalcitrance and/or toxicity and DQO of 1,013 mg L-1). The total inorganic fraction, given by the amount of total fixed solids was 3,670 mg L-1, which means 3,6 times bigger than the organic fraction. The study of leachate treatment by homogeneous catalytic ozonation was given, mainly, for the sequential use of two Taguchi\'s orthogonal arrangements, being the first, L16 design, for exploratory studies of the most important factors in the percentual reduction of DQO. The factors studied were the ozone outflow, the Fe2+, Fe3+, Zn2+, Mn2+, Ni2+ and Cr3+ ions concentration, the reaction medium pH and the presence/absence of UV radiation source UV (254 nm). Amongst the transition metals, Fe2+ and Fe3+ ions have demonstrated to be as more viable as free hydroxyl radicals catalyst due to its statistics significance (p = 0,005) and also because they have a greater tolerance to the environment discarding (less toxicity) compared to the other ions. The use of L8 Taguchi\'s orthogonal arrays gives the possibility to reach 50 % maximum COD depletion. The best factors configuration, using COD percentage reduction as experimental design response was: 5 L h-1 (589,9 mg h-1 O3) ozone outflow, 10 mg L-1 ferrous concentration, 5 mg L-1 ferric ion concentration and pH 5.