A degradação do herbicida Diuron comercial (Nortox SA) foi realizada utilizando os ânodos Ti/RuxTi(1-x)O2 e Ti/IrxTi(1-x)O2 (x = 0,3; 0,5 e 0,7). A investigação da degradação foi conduzida na presença e na ausência de cloreto. O estudo da remoção do herbicida em função da densidade de corrente na ausência de cloreto rendeu remoções de 41 e 49% de demanda química de oxigênio (DQO) e remoções de 10 e 14% de carbono orgânico total (COT) a 100 mA cm-2, respectivamente. Mantendo-se o tempo de eletrólise constante (4 h), a composição do ânodo Ti/Ru0,7Ti0,3O2 foi determinada como a mais ativa para remoção do Diuron e seus subprodutos. Com a adição de cloreto, a taxa de degradação dobrou, e obteve-se 100% de remoção de DQO para o ânodo Ti/Ru0,3Ti0,7O2. O herbicida Alaclor foi totalmente mineralizado por diferentes processos eletroquímicos oxidativos avançados (PEOAs), empregando célula eletroquímica em escala de bancada (100 mL) equipada com cátodo de difusão de ar capaz de eletrogerar H2O2 e ânodos de Pt e diamante dopado com boro (BDD). O melhor desempenho para o tratamento de 100 mL de solução Alaclor 0,60 mmol L-1 durante 360 min, foi obtido por meio do processo fotoeletro-Fenton (FEF) empregando ânodo de BDD na presença de 0,5 mmol L-1 de Fe2+. De acordo com as análises de CG-MS, a etapa de degradação do Alaclor envolveu quatro vias diferentes de reação (desalquilação, ciclização, cisão da ligação R-N e hidroxilação), resultando em nove subprodutos que, em seguida, levaram ao surgimento de ácidos carboxílicos que foram detectados. Diferentes quantidades de íons nitrogenados (NH4+ e NO3-) e clorados (Cl-, ClO3- e ClO4-) foram acumulados nas soluções finais da degradação, dependendo do ânodo e da corrente aplicada. O herbicida Diuron (0,185 mmol L-1 e pH 3,0), foi tratado também por diferentes PEOAs, como oxidação anódica com H2O2 eletrogerado (OA-H2O2), eletro-Fenton (EF) e fotoeletro-Fenton empregando luz UVA (FEF) ou FEF empregando luz solar (FEFS). Os ensaios foram realizados em uma célula eletroquímica em escala de bancada (100 mL) e em seguida testes em uma planta pré-piloto (2,5 L). Nos experimentos com célula eletroquímica em escala de bancada, o tratamento FEF empregando ânodo de BDD foi o método mais potente, produzindo 93% de mineralização após 360 min a 100 mA cm-2. Na planta de fluxo pré-piloto, o processo FEFS atingiu uma porcentagem de mineralização máxima de 70% a 100 mA cm-2. Os ácidos oxálico e oxâmico foram detectados como os ácidos carboxílicos finais e íons amônio e cloreto também foram encontrados, onde o último íon foi parcialmente convertido em íons clorato e perclorato na superfície do ânodo de BDD / Commercial herbicide Diuron solution (Nortox SA) was degrated using Ti/RuxTi(1-x)O2 and Ti/IrxTi(1-x)O2 (x = 0.3, 0.5, and 0.7) anodes. Degradation was investigated in the presence and in the absence of chloride. In the absence of chloride, herbicide removal yielded 41 and 49% COD (chemical oxygen demand) removal, and 10 and 14% TOC (total organic carbon) removal at 100 mA cm-2, respectively. For a constant electrolysis time (4 h), Ti/Ru0.7Ti0.3O2 anode composition removed Diuron and its byproduct the most activelly. Addition of chloride doubled the removal ratio, and the Ti/Ru0.3Ti0.7O2 anode afforded 100% COD removal. Electrochemical advanced oxidation processes (EAOPs) quickly degraded and even totally mineralized the herbicide Alachlor in electrochemical cells equipped with a carbonaceous air-diffusion cathode that was able to electrogenerate H2O2 and with a Pt or boron-doped diamond (BDD) anode. The photoelectron-Fenton (PEF) process with BDD in the presence of 0.5 mmol L-1 Fe2+ performed the best in Alachlor solutions treatment (100 mL, 0.60 mmol L-1, 360 min.). According to GC-MS analyses, Alachlor degradation involved four different reaction pathways (dealkylation, cyclization, R-N bond cleavage and hydroxylation), to give nine byproducts, including the detected carboxylic. Different amounts of nitrogenated (NH4+ and NO3-) and chlorinated (Cl-, ClO3- and ClO4-) ions accumulated in the final solutions depending on the anode and the applied current. The herbicide Diuron (0.185 mmol L-1 and pH 3.0) was treated using different EAOPs like anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF), and solar PEF (SPEF). Experiments were performed in 100 mL electrochemical cells, and in a 2.5 L pre-pilot flow plant. In the electrochemical cells, the PEF treatment with BDD was the most potent, yielding 93% mineralization after 360 min at 100 mA cm-2. In the pre-pilot flow plant, the SPEF process furnished maximum mineralization of 70% at 100 mA cm-2. Oxalic and oxamic acids were detected as final carboxylic acids. Ammonium and chloride ions were also released; the latter ion was partially converted into chlorate and perchlorate ions at the BDD surface

As tecnologias utilizadas em estações de tratamento de água e efluentes não são eficientes para a remoção total de resíduos farmacêuticos e os efeitos dessas substâncias sobre o meio ambiente e a saúde humana ainda não são bem conhecidos. No presente trabalho, estudou-se a degradação do antibiótico enrofloxacina (ENRO) por fotólise e pelo processo H2O2/UV na presença de compostos bio-orgânicos (BOS), que têm se apresentado como interessantes promotores da oxidação de poluentes. Os experimentos foram realizados em um reator fotoquímico tubular de imersão com fonte radiante (lâmpada de xenônio) concêntrica, operado em batelada com recirculação. Utilizaram-se concentrações iniciais de ENRO e de BOS iguais a 50 mg L-1 e 20 mg L-1, respectivamente. Para todos os pH mantidos constantes (3, 5, 7 ou 9), a solução foi irradiada por 240 minutos. Os resultados indicam que o antibiótico não sofreu hidrólise em qualquer dos pH estudados em um período de 24 horas. Por sua vez, a fotólise da enrofloxacina mostrou-se eficiente somente na presença do composto bioorgânico CVT 230 (BOS C), com remoção de ENRO de quase 90% em meio neutro (pH 7). Resultados da literatura, associados a experimento realizado em meio anóxico, sugerem a participação de oxigênio singlete como principal espécie oxidante da enrofloxacina. Por outro lado, a degradação da ENRO pelo processo H2O2/UV apresentou remoção máxima do fármaco de 48% em pH 7, o que sugere que a ação de oxigênio singlete e/ou radicais hidroxila não foi eficaz na presença de peróxido de hidrogênio. Portanto, o BOS C pode ser empregado como promotor no tratamento de águas e efluentes aquosos contaminados com enrofloxacina sob baixas potências radiantes ou em sistemas irradiados por luz solar. / The technologies used in water and wastewater treatment plants are not efficient for the total removal of pharmaceutical compounds whose effect to the environment and to human health are still not well known. In this work, the degradation of the antibiotic enrofloxacin (ENRO) was studied by photolysis and by the H2O2/UV process in the presence of bio-organic substances (BOS), which have been identified as interesting promoters of pollutant oxidation. The experiments were carried out in a tubular immersion photochemical reactor equipped with a concentric radiant source (xenon lamp), and operated in batch mode with recirculation. Initial ENRO and BOS concentrations of 50 mg L-1 and 20 mg L-1 were used, respectively. The solution was irradiated for 240 minutes for all pH studied at constant values (3, 5, 7, and 9). The results show that the antibiotic did not undergo hydrolysis at any pH after 24 hours. The photolysis of enrofloxacin showed to be efficient only in the presence of the bio-organic substance CVT 230 (BOS C), with almost 90% ENRO removal in neutral solution (pH 7). Results from the literature, associated with an experiment carried out in anoxic conditions, suggest singlet oxygen as the main species responsible for enrofloxacin oxidation. On the other hand, ENRO degradation by the H2O2/UV process showed a maximum removal of 48% at pH 7, suggesting that the action of singlet oxygen and/or hydroxyl radicals was not effective in the presence of hydrogen peroxide. BOS C can therefore be used as an efficient promoter for the treatment of enrofloxacin-containing water and wastewater under low irradiant power or in solar-irradiated systems.

Orientador: Wilson de Figueiredo Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-24T02:49:05Z (GMT). No. of bitstreams: 1 Torres_CarolinaFerreira_M.pdf: 3163293 bytes, checksum: 169b47e5a4d52ba3e29d4ad8c88bec54 (MD5) Previous issue date: 2013 / Resumo: O uso de fotocatalisadores suportados tem sido a estratégia preferencial em fotocatálise heterogênea, uma vez que a separação do material fotoativo do meio reacional é difícil e dispendiosa. A quitosana é um biopolímero de disponibilidade ilimitada, fonte renovável, é biodegradável e possui alto poder de adsorção. Esferas de quitosana impregnadas com TiO2 P-25 foram obtidas pela técnica de coagulação, onde uma mistura de quitosana e TiO2 P-25 é dissolvida em meio ácido e gotejada sobre um banho alcalino formando as esferas. Depois de lavadas e secas estas foram caracterizadas quanto à sua morfologia, resistência à solução ácida e à fotodegradação, área superficial, DRX, refletância de radiação UV/Vis e absorção de radiação IV. A atividade fotocatalítica das esferas foi avaliada utilizando solução de ácido salicílico 50 mg L. Placas de Petri contendo 0,5 g de esferas com relação quitosana: TiO2 P-25 na proporção de 1:10 (m/m) e 25 mL de solução de AS foram iluminadas por radiação UV e em intervalos de 8 horas alcançou-se mineralização de 40%, determinado por medidas de COT e emissão de fluorescência. As esferas foram reutilizadas em mais dois ciclos de ensaios de fotodegradação sem que passassem por qualquer processo de limpeza e sem perderem sua atividade fotocatalítica. / Abstract: The use of supported photocatalysts has been the preferred strategy for heterogeneous photocatalysis, since the separation of photoactive material from the reactional mean is difficult and expensive. Chitosan is a biopolymer of unlimited availability; it is a renewable source, biodegradable and has a high adsorption power. Chitosan beads impregnated with TiO2 P-25 were obtained by the coagulation technique, where a mixture of chitosan and TiO2 P-25 is dissolved in an acidic mean and dripped onto an alkaline bath, forming the spheres. Once washed and dried, they were characterized as to their morphology and resistance to acid solutions and photodegradation, as well as to their surface area, XRD, UV/Vis radiation reflectance and IR radiation absorption. The photocatalytic activity of the spheres was evaluated using salicylic acid solution 50 mg L. Petri dishes containing 0.5 g of beads with chitosan proportion: TiO2 P-25 at a ratio of 1:10 (w/w) and 25 mL of SA solution were illuminated by UV radiation and within 8-hour intervals a mineralization of 40% was reached, as determined by TOC measures and fluorescence emission. The beads were reused in two other test cycles of photodegradation without undergoing any cleaning process and without losing its photocatalytic activity. / Mestrado / Quimica Analitica / Mestra em Química

Orientador: Peterson Bueno de Moraes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-21T23:07:04Z (GMT). No. of bitstreams: 1 Silveira_JeffersonEduardo_M.pdf: 1833335 bytes, checksum: 71226fb620b38ed3dd8fd9ee6cfac08d (MD5) Previous issue date: 2012 / Resumo: A crescente degradação dos corpos d'água é assunto de constante interesse dos pesquisadores, da opinião pública e da mídia, devido à preocupação com a saúde pública, com os meios de produção e no legado às gerações futuras. Embora nos últimos anos as engenharias química, sanitária e ambiental tenham tido um significativo avanço nos métodos para tratamento de resíduos, alguns tipos de efluentes de composição complexa, como o lixiviado de aterro sanitário, não são adequadamente tratados pelos processos convencionais. Neste trabalho, propôs-se o uso da tecnologia eletroquímica, já utilizada na remedição de diversos tipos de resíduos e efluentes, para o desenvolvimento e aperfeiçoamento de um reator eletroquímico, em escala piloto, para tratamento do lixiviado do aterro sanitário do município de Limeira-SP. O lixiviado de aterro sanitário é um líquido escuro, com potencial patogênico, toxicológico e que pode conter compostos orgânicos como fenóis, pesticidas e íons metálicos. Foi utilizado um reator eletroquímico com eletrodos de titânio recobertos com 70%TiO2/30%RuO2 operando em batelada com recirculação, visando à redução da cor, carga orgânica e toxicidade. A partir dos resultados dos parâmetros físico-químico e biológicos, o sistema foi otimizado quanto à vazão, densidade de corrente, concentração de eletrólitos suporte e tempo de tratamento. Após 60 minutos de tratamento em densidade de corrente de 250 mA cm-2, concentração de eletrólito de 0,5 M de NaCl e vazão de 400 L h-1 foi possível remover 80% de DQO, 75% de N-NH3, 65% de COT e 90% de DBO. Levando-se em conta somente a remoção de amônia, a densidade de corrente mínima de 25 mA cm-2 já teve excelente desempenho após 30 minutos de tratamento. O sistema pode ser considerado economicamente viável para tratar este tipo de efluente em comparação aos tratamentos convencionais normalmente utilizados, com a vantagem de ser rápido, ocupar pouco espaço e não gerar lodo / Abstract: The increase in deterioration in the quality of water bodies is a subject of interest for researchers, public and media due to concern about public health. Although chemical engineering and environmental sciences have been experiencing lately significative advance in methods for wastewaters treatment, some types of effluents with complex composition such as landfill leachate are not adequately treated by conventional processes. In this work, we proposed the use of electrochemical technology, already used in the remediation of several types of waste and effluents, for development and improvement of an electrochemical pilot scale flow reactor for the treatment of raw landfill leachate from Limeira city, SP. The landfill leachate is a dark liquid with toxicological and pathogenic potential and may contain organic compounds such as phenols, pesticides and metallic ions. We used an electrochemical reactor with titanium oxide electrodes coated with 70% TiO2/30% RuO2 operating in batch recirculation mode, aiming to reduce color, organic load and toxicity. The electrochemical system was optimized from physicochemical and biological analyses considering the flow rate, current density, supporting electrolyte concentration and treatment time. Tests in 60 minutes at 250 mA cm-2, NaCl 0.5 M and flow rate of 400 L h-1 resulted on 80% COD, 75% NH3 - N, 65% TOC and 90% of BOD removal. Considering solely the removal of ammonia, 25 mA cm-2 was sufficed to reach a good performance in 30 minutes of treatment. The system showed be economically interesting for the treatment of this type of effluent when compared to conventional treatments normally used, because have the following advantages: higher degradation rates, small footprint, zero or low-generation of sludge / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia

Recently, an increasing problem in wastewater treatment is the insufficient removal of organic pollutants. These substances can be toxic to the environment already in a small amount, either acutely or chronically. The goal is therefore to develop of technologies that ensure their effective removal. One possibility is to use advanced oxidation processes. Advanced oxidation processes work on the principle of non-selective oxidation mediated by OH radicals. Several methods such as O3/H2O2 (Peroxone), UV/H2O2 or Fenton´s reaction can be used to generate them. The aim of this thesis was to evaluate the effectiveness of the used advanced oxidation processes in wastewater treatment via ekotoxicity tests. Wastewater samples treated with advanced oxidation processes on the pilot unit showed low values of acute toxicity for selected test organisms (D. magna, T. platyurus, S. alba, L. minor). For the sample of waste water that was treated with the UV/H2O2 on AOP laboratory unit, there was an increase in acute toxicity on the testing organism D. magna and L. minor. The similar effect was observer in the tests with the D. magna with the model samples treated with the same method, while the tests on the L. minor showed a reduction in toxicity.

This thesis deals with advanced oxidation processes (AOPs) and it’s use for removal of micropollutants from wastewater. The first chapter explains the need AOPs, water quality, pollution and substances that are present in the water. Further, the first chapter outlines approach of the current legislation to micropollutants. The second chapter explains the theory and principle of operation of AOPs. This chapter is divided into two sections. The first section describes AOPs, which were tested at selected WWTP. In the second section, there are described some other AOPs. The third chapter is a literature retrieval of AOPs dealing with the removal of micropollutants. This chapter is focused on the removal of hormones by AOPs using ozone-based AOPs. The fourth chapter describes the actual testing of selected AOPs. The chapter describes selected WWTP, pilot-scale AOP unit and test results. In the last chapter there is designed and described full-scale AOP tertiary unit for removing of micropollutants. The last chapter also contains economic analysis of the proposed tertiary unit.

<p>This dissertation investigates the factors which affect the removal of arsenic from groundwater by adsorption and coagulation technologies, including the interactions between As and natural organic matter (NOM). Humic acid (HA) was utilised as an NOM analogue, and was shown to be capable of both complexing and oxidising As, depending upon the prevailing conditions. The arsenic removing capabilities of three iron oxide coated sands (IOCS) were investigated, including IOCSW, a waste material from a local drinking water treatment plant generated during the removal of iron and manganese. IOCSW was highly effective at removing both As(V) and As(III) from synthetic water matrices (qmax = 78.3 &micro;g As(V)/g and 99.1 &micro;g As(III)/g). The negative effects of competitive anions (phosphates, silicates and HA) on arsenic removals were not significant enough to preclude the application of IOCSW for arsenic removal during drinking water treatment. The removals of both As and NOM by coagulation and enhanced coagulation with pH correction and preoxidation were also investigated. As(V) &nbsp;was more readily removed by coagulation than As(III), so that the most efficient coagulation treatment investigated for arsenic and NOM removal applied preozonation with subsequent combined coagulation with polyaluminium chloride and ferric chloride. Different groundwaters displayed large variations in the As and NOM removal behaviours. Response surface methodology (RSM) was therefore applied to investigate &nbsp;the interactions between As and NOM during ferric chloride coagulation and optimise their combined removals. Multiple interaction effects were observed during this investigation, highlighting the importance of utilizing RSM to optimise drinking water treatment technologies.</p> / <p>Ova disertacija ispituje faktore koji utiču na uklanjanje arsena iz podzemne vode primenom adsorpcija i koagulacije, uključujući i interakcije između arsena i prirodnih organskih materija (POM). Huminska kiselina (HA) je korisćena kao model za POM, a pokazano je da može i da kompleksira i da oksiduje As, u zavisnosti od eksperimentalnih uslova. Ispitivane su mogućnosti uklanjanja arsena za tri peska obložena gvožđe oksidom (IOCS), uključujući IOCSW, koji je dobijen sa postrojenja za tretman vode za piće i potiče iz procesa uklanjanja gvožđa i mangana. IOCSW se pokazao kao visoko efikasan za uklanjanje As(V) i As(III) iz sintetičkih vodenih matriksa (q_max = 78.3 &micro;g As(V)/g i 99.1 &micro;g As(III)/g). Negativni efekti kompetirajućih jona (fosfata, silikata i HA) na uklanjanje arsena nisu bili dovoljno značajni da bi se isključila primena IOCSW za uklanjanje arsena tokom tretmana vode za piće. Zajedničko uklanjanje As i POM koagulacijom i unapređenom koagulacijom uz pode&scaron;avanje pH i kombinovanje sa oksidacionim predtretmanima je takođe ispitivano. Bolje uklanjanje koagulacijom postignuto je za As(V) u odnosu na As(III), stoga se kao najefikasniji ispitivani koagulacioni tretman pokazalo uklanjanje arsena i POM primenom predozonizacije praćene kombinovanom koagulacijom sa polialuminijum hloridom i gvožđe hloridom. Ispitivanja na različitim podzemnim vodama, pokazala su velike varijacije u pona&scaron;anju As i POM tokom tretmana. Iz tog razloga je primenjena metodologija odzivne povr&scaron;ine (RSM) u cilju ispitivanja interakcija između As i POM tokom koagulacije gvožđe hloridom i optimizacije njihovog kombinovanog uklanjanja. Sagledavanje većeg broja interakcija primenom metodologije odzivne povr&scaron;ine potvrđuje važnost njegove primene pri optimizaciji tretmana vode za piće.</p>

Antibiotics are substances that inhibit the growth of microorganisms and are widely used in modern medicine. High consumption of antibiotics correlates with their elevated occurence in sewage systems, from where they are further released into the environment. The threat of their occurrence in the environment is in triggering the formation and spread of antibiotic resistance. This thesis focuses on the removal of selected antibiotics and partly on the antibiotic resistance from wastewater by advanced oxidation processes (AOPs). AOPs are based on the creation of highly reactive hydroxyl radicals, which are able to oxidize even highly persistent substances. The thesis focuses on the purification of effluents from municipal wastewater treatment plants (WWTP), which are identified as the main source of pharmaceutical pollution in the environment, by AOPs mainly based on ozonation. These processes were tested under laboratory conditions on model water as well as under real conditions as the tertiary stage of the treatment at Brno-Modřice WWTP under various operating states. As the results of the performed experiments show, it could be concluded that the studied AOPs are capable of effective degradation of studied antibiotics from the treated medium. Under real conditions, the antibiotics sulfamethoxazole, trimethoprim, azithromycin and clarithromycin were monitored. Output concentrations in each operational state were achieved to be below the limit of detection for all four antibiotics. The application of AOPs based on ozonation as the tertiary step of the treatment also had a positive effect on the reduction of microbial contamination and antibiotic resistance. Within the pilot plant experiments, a reduction of up to 4 orders of magnitude of E.coli, coliform microorganisms and a reduction of their resistant strains in the range of 1.4 - 4.0 logs were observed, compared to the effluent from the WWTP.

[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