Nos últimos anos, os processos oxidativos avançados (POAs) têm emergido como métodos potencialmente poderosos para transformar poluentes orgânicos recalcitrantes em substâncias menos tóxicas. O presente trabalho visa estudar a degradação de clorofenóis 2,4-diclorofenol (2,4-DCF) e pentaclorofenol (PCF) em solução aquosa por meio do processo foto-Fenton. Os experimentos foram realizados em um reator fotoquímico, em regime batelada, com recirculação e admissão contínua de peróxido de hidrogênio. Os efeitos das concentrações iniciais de clorofenóis, H2O2 e Fe(II), bem como, da potência da lâmpada de vapor de mercúrio, foram estudados a partir de um planejamento experimental Doehlert em multiplos níveis e analisados segundo a metodologia de superfícies de respostas. A foto-oxidação foi monitorada por medidas da concentração de carbono orgânico total (TOC) e do espectro de absorção da solução ao longo do tempo e, em alguns casos, medidas de toxicidade por meio de bioensaios com Artemia sp. Os resultados dos experimentos realizados com 2,4-DCF evidenciaram degradação gradativa, com remoções de TOC superiores a 99%, após 1 hora de tratamento, além de remoção de toxicidade, mesmo para altas concentrações iniciais do poluente (até ca. 415 mgC L-1). Nos experimentos realizados com PCF observouse decaimento inicial de TOC bastante rápido (15 minutos), o que sugere que a degradação dos clorofenóis torna-se mais rápida com o aumento do número de átomos de cloro ligados ao anel aromático. Foi removida mais da metade do TOC inicial por volta de 30 minutos de reação, obtendo-se remoções de até 90,8% ao final do tratamento. Por outro lado, comparado ao 2,4-DCF, no caso do PCF observou-se redução acentuada da taxa de remoção de TOC após esse tempo, o que pode ser explicado a partir da maior concentração de íons cloreto em solução, da formação de complexo estável desses íons com Fe(III) e de espécies geradas a partir de reações envolvendo esse complexo. No conjunto, os resultados comprovam a viabilidade do processo foto-Fenton para remediação de efluentes aquosos contendo clorofenóis. / In recent years, advanced oxidation processes (AOP) have emerged as potentially powerful methods to transforming organic pollutants into harmless substances. The present work aims to study the degradation of chlorophenols (2,4-dichlorophenol and pentachlorophenol) in aqueous solution by the photo-Fenton process. The experiments were conducted in a batch recycle photochemical reactor with continuous feed of hydrogen peroxide solution. The effects of the initial concentrations of chlorophenols, H2O2, and Fe(II), as well as of the electric power of mercury vapor lamp, were studied by means of a Doehlert multivariate experimental design at multiple levels. Experimental results were analyzed according to the response surface methodology. In order to characterize the degradation of the pollutant, time-measurements of the total organic carbon concentration (TOC) as well as the absorbance spectra of the solution, were carried out. In some cases toxicity bioassays were carried out with Artemia sp. The results obtained from experiments with 2,4-dichlorophenol showed a gradual degradation, with more than 99% of TOC removals after 1 hour of treatment, along with toxicity removal, even for high initial pollutant concentrations (ca. 415 mgC L-1). In the case of pentachlorophenol, a fast initial TOC decrease (around 15 minutes) was observed, suggesting that chlorophenols degradation becomes faster with the increment of chloro atoms number bounded to the aromatic ring. More than a half of the initial TOC was removed around 30 minutes of reaction, rising 90.8% of TOC removal at the end of the treatment. In the other hand, comparing to 2,4-DCF, for PCF a marked reduction of the maximum rate of TOC removal after that time. This can be explained by higher concentrations of chloride ions in the solution, for the formation of stable complexes with Fe(III) ion and resulting species in reaction involving such complexes. As a whole, the results confirm the effectiveness of the photo-Fenton process for the remediation of aqueous solutions containing chlorophenols.

This PhD thesis investigated solid and liquid waste treatment systems for Sureclean, a waste Management company based in the North of Scotland. Sureclean receives a diverse range of waste streams and the increasing need for sustainable development as well as stringent environmental legislation motivated this research to develop an integrated waste treatment system. Waste characterisation was conducted using a range of analytical instrumentation to identify the TPH, COD, heavy metals content, TOC, and particle size of Sureclean waste streams. From there, four treatment systems were investigated utilising Sureclean waste streams: mechanical separation, chemical treatment, electro-coagulation and the advanced oxidation process. Laboratory and field trials were conducted using these different treatment techniques and the analysis was performed to verify the treatment results. The result of these trials led to the development of four modular waste treatment units, that form the outcome of this research: the Sureclean Water Treatment System (SWTS), a filtration based mechanical separation system was shown to reduce the TSS, BOD and TOC content of an oily wastewater; the Sureclean Sludge Separation System (SSSTS), a chemical-enhanced filtration based system was demonstrated to reduce 52.6 % of the sewage sludge volume; the Sureclean Electro-coagulation Water Treatment System (SEWTS), a system that agglomerates colloid particles and demulsifies oil removed 99.9 % of TPH from Sureclean interceptor effluent; and the Sureclean Advanced Water Treatment System (SAWTS), an advanced oxidation process which was demonstrated to reduce the TPH of a contaminated groundwater collected from an ex-gas work. The treated effluent could be discharged to Sureclean interceptor. The four treatment units developed in this research expanded Sureclean waste treatment capabilities and an integrated system was developed to treat different waste streams and to improve the treatment efficiency thus increasing the revenue and future waste stream options for Sureclean.

Adequate wastewater management is a crucial element to achieve water sustainability in the petroleum refining sector, as their operations produce vast quantities of wastewater with potentially harmful contaminants. Treatment technologies are therefore pivotal for stopping these chemicals from entering the environment and protecting receiving environments. However, refining effluents are still linked to serious pollution problems, partly because little progress has been made in determining the causative agents of the observed biological effects, resulting in non-targeted treatment. Here it is shown that naphthenic acids, which have been reported as toxic and recalcitrant, are important components of refining wastewater resulting from the processing of heavy crude oil and that they have a significant contribution to the toxic effects exerted by these effluents. Furthermore, it was found that their chemical stability makes them highly resistant to remediation using Pseudomonas putida and H2O2/Fe-TAML (TetraAmido Macrocyclic Ligands) systems under laboratory conditions, and only sequential aliquots of Fe-TAML catalysts and H2O2 showed to partially degrade naphthenic acids (50 mg/L) within 72 hours. Results suggest that a combinatorial approach of Fe-TAML/H2O2 followed by biodegradation might improve current treatment options, but further optimisation is required for the biological treatment. These results can serve as a starting point for better environmental regulations relevant to oil refining wastewater resulting from heavy crude oil, as naphthenic acids are not currently considered in the effluent guidelines for the refining sector. Furthermore, the degradation of naphthenic acids under mild conditions using Fe-TAML/H2O2 systems indicates that these catalysts hold promise for the remediation of refining wastewater in real-life scenarios.

No processo UV/H2O2, oxidar o substrato a CO2 e água resulta em um elevado consumo de H2O2. Então, esse processo tem sido proposto como um pré-tratamento para reduzir a toxicidade a níveis seguros para o tratamento biológico posterior. Por essa razão, é necessário estudar o progresso da reação, pois a toxicidade de alguns intermediários formados durante a oxidação pode ser mais elevada que a do composto inicial. Neste trabalho, os experimentos foram realizados em um reator tubular fotoquímico, contendo em seu eixo uma lâmpada de vapor de mercúrio de baixa pressão, conectado a um tanque de recirculação. O processo UV/H 2O2 é aplicado no tratamento de água contendo fenol (50500mg C.L-1). Os resultados demonstraram que o principal produto da oxidação primária é o catecol, indicando que a hidroxilação ocorre predominantemente na posição orto. A abertura do anel aromático leva à formação de ácidos orgânicos, o que explica a diminuição do pH durante a reação. Foram identificados os seguintes ácidos: fórmico, oxálico, maleico e malônico. Na etapa seguinte desse trabalho, dois modelos cinéticos foram desenvolvidos. Os modelos foram baseados nas reações químicas e fotoquímicas iniciadas pelos radicais hidroxila gerados pela fotólise do peróxido de hidrogênio. Foram utilizados os valores encontrados na literatura para os parâmetros fotoquímicos e constantes cinéticas das reações fotoquímicas. Os resultados experimentais foram utilizados para estimar as constantes cinéticas das reações que envolvem os compostos aromáticos. No primeiro modelo foram contempladas todas as reações fotoquímicas envolvidas e, no segundo, apenas as consideradas mais significantes. Os resultados das simulações considerando os parâmetros ajustados mostraram uma melhor concordância com os dados experimentais para o primeiro modelo. As constantes cinéticas deste modelo para as reações nas quais o fenol é oxidado a catecol (k14) e hidroquinona (k15) foram 2,60x108L.mol-1.s-1 e 1,03x108L.mol-1.s-1, respectivamente. As constantes cinéticas para a oxidação do catecol (k17) e hidroquinona (k18) encontradas foram 1,41x108L.mol-1.s-1 e 2,02x108L.mol-1.s-1, respectivamente. Também foi observada elevada correlação entre as constantes k14 e k17 e entre k15 e k18. / In the UV/H2O2 process, the oxidation of the substrate to CO2 and water results in high H2O2 consumption. Due to this fact the process has been proposed as a pretreatment to reduce toxicity to safe levels prior to biological treatment. Thus, it is necessary to study the reaction progress because some intermediate compounds may be more toxic than the initial compound. In the present study experiments were carried out in a lab-scale tubular photochemical reactor with a low-pressure mercury vapor lamp placed in its axis, connected to a recirculation tank. The UV/H2O2 process was applied to the degradation of an aqueous solution containing phenol as a model pollutant (concentration range: 50-500mg.L-1). The experimental results indicated that orto-hydroxylation (catechol formation) was predominant. The cleavage of the aromatic ring resulted in the production of organic acids, which caused the pH decrease over the reaction time. The following acids were detected: formic, oxalic, maleic and malonic. The experimental results were used to estimate kinetic rate constants for the reactions involving aromatic compounds according to two kinetic models based on chemical and photochemical reactions, initiated by hydrogen peroxide photolysis to produce hydroxyl radical. Numerical values of chemical reaction rate constants and photochemical parameters were taken from literature. The first model considered all photochemical while the second model considered the most significant ones. The parameter fitting results showed better agreement with experimental values based on the first model. The resulting values for the rate constants according to this model were as follows: 2.60x108L.mol-1.s-1 for phenol oxidation to catechol, and 1.03x108L.mol-1.s-1 for phenol oxidation to hydroquinone by hydrogen peroxide. The reaction rate constants for the oxidation of catechol, and hydroquinone by hydrogen peroxide are 1.41x108L.mol-1.s-1 and 2.01x108L.mol-1.s-1, respectively. A high correlation was observed between constants k14 and k17, and between k15 and k18.

O efluente fenólico em estudo apresenta a relação DBO5/DQO (Demanda Bioquímica de Oxigênio/ Demanda Química de Oxigênio) igual a 0,15, ou seja caracteriza-se por ser um efluente não biodegradável. No tratamento inicial do efluente utilizou-se ozônio, na presença do sal de ferro II proveniente da solução de sulfato ferroso heptaidratado 0,82 mol. L-1 e do peróxido de hidrogênio , que possui a finalidade catalítica na formação dos radicais hidroxilas, com alto poder de oxidação da matéria orgânica. Nesta etapa foi estudado a união dos processos oxidativos O3/UV e Foto-Fenton, Foram tratados 3 L do efluente fenólico in natura em um reator fotocatalítico com lâmpada ultravioleta. Em todos os experimentos o pH e a temperatura do meio reacional foram controlados. Os experimentos foram executados segundo um planejamento de Taguchi L16, no qual a variável entrada de maior importância para a degradação da matéria orgânica foi o peróxido de hidrogênio. As variáveis respostas analisadas foram a concentração do Carbono Orgânico Total, Demanda Química de Oxigênio e Fenóis Totais. No planejamento de Taguchi L16 foram selecionadas as variáveis significativas para o processo de degradação do efluente fenólico, a fim de serem otimizadas através do Método de Superfície de Resposta (MSR Foto-Fenton e O3/UV). O método de otimização MSR Foto-Fenton foi eficiente na degradação do composto fenólico, sendo assim a melhor condição experimental da planilha de otimização foi a de número 10 e corresponde a uma redução de COT= 54,68%, DQO=78,73% e Fenois Totais= 98,1%. Os parâmetros controlados do processo para essa condição foram: pH=3, temperatura de 30 ºC, potência ultravioleta de 28 W e reagente Fenton (H2O2= 48,3g e Fe+2 =5,95g), que corresponde a relação mássica H2O2 /Fe+2 igual a 8. / The phenolic effluent in this study has the rate DBO5/DQO (Biochemical Oxygen Demand / Biochemical Oxygen Demand) equal to 0.15, which is characterized by an effluent to be non-biodegradable. In the initial treatment of phenol was used ozone in the presence of iron salt II from the solution of ferrous sulfate heptahydrate 0.82 mol. L-1 and hydrogen peroxide, which has the purpose in the catalytic formation of hydroxyl radicals with high oxidation power of organic matter. In this stage, was studied the union of the oxidative process O3/UV and Photo-Fenton. The effluent was treated about 3 L about in a photocatalytic reactor with UV lamp. In all experiments, the pH and temperature of the reaction medium were control. The experiments are being carried out to a Taguchi L16 design, in which the input variable of greatest importance to the degradation of organic matter was hydrogen peroxide. The response variable analyzed was given by the concentration of Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD) and Total Phenols (FT). In planning Taguchi L16 significant variables were selected for the degradation process of phenolic wastewater in with purpose of to be optimized by Response Surface Method (RSM Photo-Fenton and O3/UV). The optimization method was efficient photo-Fenton degradation of phenolic compound, so the best experimental condition spreadsheet optimization was the number 10 and corresponds to a reduction of TOC = 54.68%, COD = 78,73% and Total Phenols= 98.1%. The controlled process parameters for this condition were: pH = 3, temperature of 30 ° C, power of 28 W ultraviolet and Fenton reagent (H2O2= 48,3g and Fe+2 = 5,95g), corresponding to mass ratio H2O2 / Fe +2 = 8.

O lodo gerado em processos de galvanoplastia é classificado pela ABNT NBR 10.004/04 como perigoso (classe I). Na literatura encontram-se poucos estudos referentes à recuperação do cromo presente no lodo gerado em sistemas de tratamento de efluentes de indústrias de galvanoplastia. Neste sentido, o presente estudo avaliou a remoção do cromo presente no lodo de galvanoplastia por meio de dois processos, visando avaliar à eficiência técnica e a viabilidade econômica de ambos. O Processo 1 consistiu na remoção do cálcio utilizando o ácido cítrico, seguida de lixiviação ácida. Na etapa de oxidação, variou-se a temperatura em 40ºC, 60ºC e 80ºC e no tempo de 30, 60 e 90 minutos, tendo em vista que a eficiência do processo de oxidação depende da temperatura e tempo. Nesta etapa do processo as concentrações de peroxido de hidrogênio (H2O2) utilizadas foram de 1,50, 3,00 e 4,50 mol.L-1. O Processo 2 realizou a oxidação do cromo sem efetuar as etapas de extração do cálcio e a lixiviação ácida. A oxidação do cromo ocorreu pelo mesmo método apresentado no Processo 1. A caracterização elementar da amostra determinou que o principal elemento constituinte do lodo é o cálcio (20,05% em massa), e que dentre os metais pesados destacam-se o cromo e o níquel (6,52% e 4,33% em massa, respectivamente). A maior eficiência de remoção do cálcio foi obtida na razão mássica de 8,00 (ácido cítrico/hidróxido de cálcio), com 51,76% em massa, seguida pela razão mássica de 5,50 com 36,75% em massa e 2,50 com 24,83% em massa. O melhor resultado de oxidação do cromo no Processo 1 foi obtido com tempo de 30 minutos, temperatura de 60ºC e concentração de peroxido de hidrogênio de 3,00 mol.L-1, com eficiência de 41,09% em massa. No Processo 2, obteve-se a remoção de 37,96% em massa de cromo a temperatura de 80ºC, por uma hora e 3,00 mol.L-1 de peróxido de hidrogênio. Avaliando os custos para remoção do cromo dos dois processos, determinou-se que o Processo 1 foi mais oneroso que o 2, porém ambos não apresentaram viabilidade econômica para aplicação em escala industrial. Nos dois processos efetuou-se a oxidação do cromo presente no lodo de galvanoplastia, permitindo a sua remoção parcial neste resíduo. Com isso obtiveram-se ganhos ambientais, pela diminuição deste elemento no resíduo de galvanoplastia, que na maioria das vezes é disposto em aterros classe I, gerando um passivo ambiental. / The sludge generated in electroplating processes is classified by NBR 10.004/04 as a hazardous material (class I). In the literature, few studies report the recovery of chromium present in the electroplating sludge generated in the industries. In this sense, the present study conducted the removal of chromium in the electroplating sludge through two different processes, aiming to evaluate their efficiency and economic viability. The first process removed calcium through the use of citric acid being performed by varying the ratio of citric acid/calcium hydroxide (2.5, 5.5 and 8.0). Then, were performed the leaching of the samples. According to the literature, the efficiency of the oxidation process varies depending on the reaction temperature, time and concentration of hydrogen peroxide. For this reason, samples were heated to a temperature ranging from 40°C, 60°C and 80°C. Also, were conducted variations in the concentrations of hydrogen peroxide (1.5, 3.0 and 4.5 mol.L-1) and reaction time (30, 60 and 90 minutes). The second Process consisted in the chrome recovery by using the galvanic sludge without removal of the calcium and acid leaching. The chrome oxidation occurred by the same method shown in Process 1. Elemental characterization of the samples determined that the primary sludge constituent was calcium (20.05% by weight), and in terms of heavy metals, the chromium and the nickel (6.52% and 4.33% by mass, respectively). Most of calcium removal efficiency was obtained at a rate of 8 with 51.76% by mass, then the ratio of 5.50 to 36.75% by mass and 2.50 to 24.83% by mass. The best oxidation result of chromium in Process 1 was obtained using a time of 30 minutes, 60°C and hydrogen peroxide concentration of 3 mol.l-1, with 41.09 wt% efficiency. In Process 2 was obtained the removal of 37.96% by mass of chromium temperature of 80°C, for one hour and 3,00 mol.l-1 of hydrogen peroxide. Evaluating the costs for chrome removal of the two processes was determined that the Process 1 was more costly than 2, but both showed no economic feasibility for implementation on an industrial scale. However, in both cases occurred the oxidation of chromium present in the electroplating sludge, allowing its removal from the residue. Thus, environmental gains have been achieved by the reduction of this element in electroplating waste, which mostly is intended for landfill class I, generating an environmental liability.

O processo de adsorção por carvão ativado é uma técnica muito aplicada para tratamento de efluentes. Porém o tratamento que envolve adsorção não é um sistema completo, pois há a necessidade da destruição dos compostos que foram imobilizados na superfície do carvão. Frente a esse problema, métodos alternativos de regeneração de carvão ativado são investigados. Os processos Fenton e foto-Fenton são considerados tecnologias promissoras de tratamento de efluentes, e foram testados para regenerar o carvão ativado. Este trabalho objetiva estudar a adsorção de fenol em carvões ativados (CAs) e a consecutiva regeneração in-situ do carvão pela oxidação de (foto-) Fenton. Duas operações diferentes foram realizadas: 1) sistema de batelada, a fim de investigar a influência das concentrações de Fe2+ e H2O2; 2) adsorção contínua em leito fixo, seguido de circulação em batelada dos reagentes de Fenton pelo leito de CA saturado, para examinar a eficiência do processo real. Foram estudados dois tipos de carvão ativado: CA L27 (meso e microporoso) e CA S23 (somente microporoso). No reator de batelada as melhores condições encontradas para a mineralização do poluente no sistema Fenton homogêneo não são as melhores para a regeneração do CA: foi observada uma redução contínua da capacidade de adsorção do L27 após 3 oxidações, devido à redução tanto da massa do CA quanto da área superficial. Uma maior concentração de Fe2+ e menor concentração de H2O2 (2 vezes a estequiometria) levou a uma recuperação de 50% da capacidade de adsorção inicial em pelo menos 4 ciclos consecutivos para o L27, enquanto que cerca de 20% para o S23. No processo consecutivo de adsorção contínua/oxidação de Fenton em batelada, a eficiência de regeneração atinge de 30% a 40% para o L27 após dois ciclos independente da concentração da alimentação e menos de 10% para o S23. O processo foto-Fenton realizado para o L27 levou à quase completa mineralização e aumentou a recuperação da capacidade de adsorção do CA (56% após dois ciclos). / The adsorption process by active carbon is a technique applied extensively for wastewater treatment. However the tertiary treatment involving adsorption is not a complete system, since there is a need of destruction of the compounds that were immobilized on the carbon surface. In face of this problem, some alternative regeneration methods of active carbon are investigated. Fenton and photo-Fenton processes have been considered promising technologies for wastewater treatment and have been tested to regenerate the AC. The purposes of this study are the adsorption of phenol on activated carbons (ACs) and the consecutive in-situ regeneration of carbon by (photo-) Fenton oxidation. Two different operations have been carried out: 1) batch procedure in order to investigate the influence of Fe2+ and H2O2 concentrations; 2) continuous fixed bed adsorption, followed by a batch circulation of the Fentons reagent through the saturated AC bed, to examine the efficiency of the real process. Two different activated carbons have been also studied: a both micro- and mesoporous AC (L27) and an only microporous one (S23). In the batch reactor the best conditions found for pollutant mineralization in the homogeneous Fenton system are not the best for AC regeneration: a continuous reduction of adsorption capacity of L27 is observed after 3 oxidations, due to the decrease of both AC weight and surface area. Higher concentration of Fe2+ and lower concentration of H2O2 (2 times the stoechiometry) lead to a 50% recovery of the initial adsorption capacity during at least 4 consecutive cycles for L27, while about 20% for S23. In the consecutive continuous adsorption/batch Fenton oxidation process, the regeneration efficiency reaches 30% to 40% for L27 after two cycles whatever the feed concentration and less than 10% for S23. A photo- Fenton test performed on L27 shows almost complete mineralization (contrary to dark Fenton) and further improves recovery of AC adsorption capacity although not complete (56% after two cycles).

O descarte de embalagens vazias dos agrotóxicos sem fiscalização e controle pode gerar problemas ambientais, afetando a saúde do homem, dos animais e da vida silvestre. Entre os inseticidas comerciais, o clorpirifós tem uma importância significativa por ser amplamente utilizado e persistente no ambiente. O ataque do radical hidroxila, OH é o processo mais eficiente de oxidação química de compostos orgânicos. A degradação de clorpirifós induzida por radiação gama foi estudada em amostras de água e em embalagens de polietileno. Embalagens de polietileno de alta densidade coextrudada em camadas sobrepostas, COEX, contaminadas com clorpirifós foram irradiadas com radiação gama em fonte de Co-60 do tipo \"Gammacell\" e do tipo \"irradiador de grande porte\". As análises de clorpirifós e solventes, assim como dos subprodutos formados foram realizadas por cromatografia a gás associada à espectrometria de massa. A radiação ionizante se mostrou uma técnica eficiente na degradação do inseticida clorpirifós nestas embalagens. / The discharge of empty plastic packaging of pesticides can be an environmental concern causing problems to human health, animals and plants if done without inspection and monitoring. Among the commercial pesticides, chlorpyrifos has significant importance because of its wide distribution and extensive use and persistence. The hydroxil OH atack is the most efficient process of chemical oxidation. The radiation-induced degradation of chlorpyfifos in liquid samples and in polyethylene pack was studied by gamma-radiolysis. Packaging of high density polyethylene tree layer coextruded, named COEX, and water samples contaminated with chlorpyrifos, were irradiated using both, a multipurpose Co-60 gamma irradiator and a gamma source with 5,000 Ci total activity, Gammacell type. The chemical analysis of the chlorpirifos and by-products were made using a gas chromatography associated to the mass spectrometry. Gamma radiation was efficient for removing chlorpyrifós from the plastic packaging in all studied cases.

Estudou-se a degradação dos fármacos acetaminofeno (ACT), atenolol (ATL), bezafibrato (BZF), diclofenaco (DIC) e ibuprofeno (IBU) em solução aquosa através de fotólise e peroxidação fotoassistida. As soluções foram caracterizadas antes e após os processos de fotólise e UV/H&#8322O&#8322 quanto à degradação dos fármacos e à remoção de carbono orgânico total. Também foi avaliada a degradação por fotólise dos fármacos em uma matriz real (efluente de estação de tratamento de esgoto, ETE). Os experimentos foram realizados em um reator anular com lâmpada de vapor de mercúrio de baixa pressão de 36 ou 75 W e concentrações iniciais de 5 ou 20 mg L&#8315&#185 de cada fármaco, em mistura e individualmente, no caso dos estudos de fotólise UV. Os resultados mostraram absorção de radiação UV (254 nm) pelo ACT superior à dos demais fármacos (&#8364=8990 L mol&#8315&#185 cm&#8315&#185), e comparativamente inferior para o ATL e IBU (&#8364=725 e 1080 L mol&#8315&#185 cm&#8315&#185, respectivamente). Não houve degradação por hidrólise após 24h em qualquer pH. O DIC e o BZF degradaram-se mais rapidamente, independentemente do processo fotoassistido. As concentrações de DIC nos experimentos realizados com [DIC]0=5 mg L&#8315&#185 ficaram abaixo do limite de detecção após 20 minutos de irradiação. Na presença de H H&#8322O&#8322 as concentrações dos contaminantes ficaram abaixo do limite de detecção após 50 minutes para concentrações iniciais de 20 mg L&#8315&#185. Os resultados dos ensaios de toxicidade nos experimentos realizados com a mistura de fármacos mostraram valores de CE50 inferiores aos valores obtidos nos experimentos com a solução dos fármacos individuais. Os valores de TOC apresentaram redução de até 13% ao final de 120 minutos, o que comprova a persistência dos produtos de degradação. A degradação por fotólise UV do ATL e do ACT ocorreu mesmo em efluente de ETE, sendo a eficiência desse processo semelhante à obtida usando-se água como matriz. Esses resultados são úteis para compreensão da remediação de águas e efluentes contendo esses contaminantes emergentes por meio de processos foto-oxidativos. / This work aimed at studying the degradation of the following pharmaceutical compounds in aqueous solution by means of photolysis and photoassisted peroxidation: acetaminophen (ACT), atenolol (ATL), bezafibrate (BZF), diclofenac (DIC), and ibuprofen (IBU). Solutions were characterized before and after photolysis and UV/H2O2 processes regarding drug degradation and total organic carbon removal. In addition, the photolysis of the pharmaceutical compounds was investigated in a real wastewater matrix (effluent from a sewage treatment plant, STP). The experiments were carried out in an annular photochemical reactor equipped with a low pressure mercury lamp (36 or 75 W) and initial solution concentrations of 5 and 20 mg L-1 of each drug, for the mixture and individual compounds, in the case of UV photolysis studies. The results revealed higher absorption of UV radiation (254 nm) by ACT than that shown by the other pharmaceutical compounds (=8990 L mol-1 cm-1), and comparatively lower for ATL and IBU (=725 and 1080 L mol-1 cm-1, respectively). No hydrolysis was observed after 24 hours at any pH. The degradation of DIC and BZF was faster, regardless the photoassisted process. DIC concentrations in the experiments carried out with [DIC]0=5 mg L-1 were below the detection limit after 20 minutes of irradiation. In the presence of H2O2, contaminant concentrations were below the detection limit after 50 minutes of irradiation for initial concentrations of 20 mg L-1. The results of the toxicity assays for the experiments carried out with the mixture of pharmaceutical compounds showed CE50 values lower than those obtained with the compounds individually. TOC removals up to 13% after 120 minutes were obtained, therefore confirming the formation of persistent degradation products. In the case of ATL and ACT, UV degradation occurred even in STP wastewater and the efficiency of the process was similar to that obtained with pure water. The results obtained in this study are useful to understand the treatment of water and wastewater contaminated with this class of emerging pollutants by means of photo-oxidative process.

In this work, a series of simple, rapid and effective photoelectrochemical methodologies have been developed and successfully applied to the study of kinetic and thermodynamic characteristics of photocatalytic oxidation processes at TiO2 nanoparticulate films. As an application of the systematic studies of photocatalytic processes by photoelectrochemical techniques, a rapid, direct, absolute, environmental-friendly and accurate COD analysis method was successfully developed. In this work, the TiO2 nanoparticles colloid was prepared by the sol-gel method. The TiO2 nanoparticles were immobilized onto ITO conducting glass slides by dip-coating method. Thermal treatment was carried out to obtain nanoporous TiO2 films of different structures. At low calcination temperature (below 600°C), nanoporous TiO2 films of pure anatase phase were prepared. At high calcination temperature (above 600°C), nanoporous TiO2 films of mixed anatase and rutile phases were obtained. At these film electrodes, the work was carried out. By employing steady state photocurrent method and choosing phthalic acid as the model compound, the photocatalytic activity of the TiO2 nanoporous films calcined at various temperatures and for different lengths of time was evaluated. It was found that the films with mixed anatase and rutile phases calcined at high temperature exhibited high photocatalytic activity. Based on semiconductor band theory, a model was proposed, which explained well this finding. By employing linear sweep voltammetry (under illumination) and choosing glucose (an effective photohole scavenger) as a model compound, the characteristics of the photocatalytic processes at nanoparticulate semiconductor electrodes were investigated. Characteristics of the nanoporous semiconductor electrodes markedly different from bulk semiconductor electrodes were observed. That is, within a large range of electrode potentials above the flat band potential the electrodes behaved as a pure resistance instead of exhibiting variable resistance expected for bulk semiconductor electrodes. The magnitude of the resistance was dependent on the properties of the electrodes and the maximum photocatalytic oxidation rate at TiO2 surface determined by the light intensity and substrate concentration. A model was proposed, which explained well the special characteristics of particulate semiconductor electrodes (nanoporous semiconductor electrodes). This is the first clear description of the overall photocatalytic process at nanoparticulate semiconductor electrodes. The investigation set a theoretical foundation for employing photoelectrochemical techniques to study photocatalytic processes. By using the transient technique (illumination step method analogous to potential step method in conventional electrochemistry), the adsorption of a number of strong adsorbates on both low temperature and high temperature calcined TiO2 nanoporous films was investigated. Similar adsorption characteristics for different adsorbates on different films were observed. In all the cases, three different surface bound complexes were identified, which was attributed to the heterogeneity of TiO2 surface. The photocatalytic degradation kinetics of the pre-adsorbed organic compounds of different chemical nature was also studied by processing the photocurrent-time profiles. Two different photocatalytic processes, exhibiting different rate characteristics, were observed. This was, again, attributed to the heterogeneity of the TiO2 surface corresponding to heterogeneous adsorption characteristics. The catalytic first order rate constants of both fast and slow processes were obtained for different organic compounds. It was found that for different adsorbates of different chemical nature the magnitudes of rate constant for the slow kinetic process were very similar, while the magnitudes of rate constant for the fast process were significantly affected by the photohole demand characteristics of different adsorbates. Photohole demand distribution that depends on the size and structure of the adsorbed molecules was believed to be responsible for the difference. By employing steady state photocurrent method, the photocatalytic degradation kinetic characteristics of both strong adsorbates and weak adsorbates of different chemical structures were compared at pure anatase TiO2 nanoporous TiO2 films as well as at anatase/rutile mixed phase TiO2 nanoporous film electrodes. At the former electrodes for all the different organic compounds studied, the photocatalytic reaction rate increased linearly with concentration at low concentrations. Under such conditions, it was demonstrated that the overall photocatalytic process was controlled by diffusion and was independent of the chemical nature of organic compounds. However, the linear concentration range and the maximum photocatalytic reaction rate at high concentrations were significantly dependent on the chemical nature of the substrates. This was explained by the difference in the interaction of different organic compounds with TiO2 surface, the difference in their photohole demand distributions at the TiO2 surface and the difference in their nature of intermediates formed during their photocatalytic mineralization. In contrast, at the latter electrodes for the photocatalytic oxidation of different organic compounds the linear ranges (diffusion control concentration range) and the maximum reaction rates at high concentration were much larger than at the former electrodes and much less dependent on the chemical nature of the organic compounds. The spatial separation of photoelectrons and photoholes (due to the coexistence of rutile phase and anatase phase) and the increase in the lifetime of photoelectrons and photoholes are responsible for the excellent photocatalytic activity of the electrodes. By employing the thin-layer photoelectrochemical technique (analogous to the thin-layer exhaustive electrolytic technique), the photocatalytic oxidation of different organic compounds at the mixed phase TiO2 nanoporous electrodes were investigated in a thin layer photoelectrochemical cell. It was found that the charge derived from exhaustive oxidation agreed well with theoretical charge expected for the mineralisation of a specific organic compound. This finding was true for all the compounds investigated and was also true for mixtures of different organic compounds. The photocatalytic degradation kinetics of different organic compounds of different chemical identities in the thin layer cell was also investigated by the photoelectrochemical method. Two kinetic processes of different decay time constants were identified, which were attributed to the degradation of preadsorbed compounds and the degradation of compounds in solution. For the degradation of compounds in solution, a change in the overall control step from substrate diffusion to heterogeneous surface reaction was observed. For different organic compounds, the variation of the rate constant was determined by the photohole demand rather than by the chemical identities of substrates. The kinetics of the fast kinetic process, on the other hand, was greatly affected by the adsorption properties of the substrates. For the strong adsorbates, the rate was much larger than for weak adsorbates. However, the rate constant of the process was independent of the chemical identities of the substrates and the variation of the constant was also determined by the photohole demand. Based on the principles of exhaustive photoelectrocatalytic degradation of organic matter in a thin layer cell, a novel, rapid, direct, environmental-friendly and absolute COD analysis method was developed. The method was tested on synthetic samples as well as real wastewater samples from a variety of industries. For synthetic samples with given compositions the COD values measured by my method agree very well with theoretical COD value. For real samples and synthetic samples the COD values measured by my method correlated very well with those measured by standard dichromate COD analysis method.