The adsorption of methylene blue onto two types of commercial activated carbons, a mesoporous type (Norit CA1) and microporous type (207C) was analysed. Powdered TiO2 was mixed with the carbon and added to the dye solution to determine the influence of the photocatalyst during the adsorption process. Equilibrium and kinetics experiments were done with and without any addition of photocatalytic titanium dioxide (TiO2). Changes in capacity, heterogeneity, and heat of adsorption were detected and related to changes in the quantity of TiO2 added by evaluating the equilibrium parameter from 13 isotherm models. The influence of TiO2 on the adsorption kinetics of the dye was correlated using simplified kinetic-type model as well as mass transfer parameters. Using a formal design of experiments approach responses such as the removal of the dye, variation of pH, external mass transfer rate (KF) and intraparticle rate constant (Ki) were evaluated. Results indicated that TiO2 increased the uptake of methylene blue onto CA1, increased Ki and CA1-TiO2 interactions had electrostatic nature. In contrast, TiO2 was seen to inhibit the equilibrium adsorption for 207C by reducing its capacity. The 207C-TiO2 interaction was attributed to a specific adsorption of TiO2 on the coconut-based adsorbent, as zeta potential and pH measurements seemed to suggest. The regeneration of activated carbon using UV-C/TiO2 heterogeneous photocatalysis in a novel bell photocatalytic reactor, and in a standard-type coiled-tube photoreactor was also studied. Initially, response surface methodology was applied to finding the optimum conditions for the mineralization of methylene blue in both reactors using methylene blue as model compound and TiO2 as photocatalyst performing direct photocatalytic decolourization. Methylene blue concentration, TiO2 concentration and pH were the variables under study. Complete mineralization of the dye was achieved in the coiled-tube reactor using 3.07 mg/L of methylene blue at pH 6.5 with 0.4149 g/L TiO2. The regeneration experiments in the coiled-tube photoreactor were done using One Variable at Time (OVAT) method. The effect of the mass of TiO2 was the only studied variable. The study indicated an increase in regeneration of CA1 and a decrease in the pH during the oxidation step at higher concentration of the photocatalyst. In the case of the regeneration of 207C, the addition of TiO2 lowered the regeneration and made the suspension more basic during the photocatalytic step. However these results were not statistically significant. Experiments using the bell photoreactor were performed applying the same response surface method used in direct photocatalytic decolourization (control). The variables under study were pH, concentration of dye-saturated carbon and TiO2 concentration. The regeneration percentage was the chosen response. Low regeneration percentages were achieved (maximum 63%), and significant differences (95% confidence interval) were found between the regeneration of the activated carbons, being higher in the case of powdered CA1 as compared with granular 207C.

Traditional occupational hygiene assessment of occupational exposures to organic gases and vapours rely on low flow (<200 ml/min) NIOSH sorbent tubes. This work investigates 3M charcoal filter media (JK50 and JK40, 3M, Inc.) for collection and analysis of organic vapours across 0.1-5 l/min. To enable this work, a custom exposure facility was constructed and validated within which organic analyte gas/vapour concentrations could be introduced at known concentrations while controlling environmental variables such as temperature and humidity and other variables. This facility enabled experiments designed to investigate collection and desorption efficiencies across a range of sample flow rates, temperature and humidity conditions for both NIOSH sorbent tubes (e.g. SKC tube) and 3M charcoal filter media. As a result of the investigations described in this thesis, the following conclusions are drawn. Performance of the 3M charcoal filter media for collection and desorption efficiencies for loading, storage time, humidity and breakthrough at low flow rates (<0.5 l/min) were found comparable to the SKC sorbent tube. It is concluded that 3M charcoal media (JK50 and JK40) are suitable for sampling and analyses of hydrocarbons at flow rates <0.5 l/min. The collection efficiencies of the 3M charcoal filter media were investigated at high flow rates (>0.5l/min) for the same parameters, i.e., loading, temperature and humidity. It is concluded that 3M charcoal filter media can be used with confidence in sampling and analysis of airborne hydrocarbons up to 5 l/min. The Wheeler-Jonas model was found to satisfactorily predict the adsorption kinetics of the 3M charcoal filter media at different loading values of hydrocarbons. It was therefore concluded that the model can be applied to determine the suitable amount of 3M charcoal filter media prior to sampling for a given loading.

The price of crude glycerol has significantly decreased worldwide because of its oversupply. Many chemical and biological processes have been proposed to transform glycerol into numerous value-added products, such as glycolic acid, 1,3-propanediol (1,3-PDO), 1,2-propanediol (1,2-PDO), glyceric acid, and lactic acid. However, these processes suffer from several drawbacks, including high production cost. Therefore, in this study, a simple and robust electrochemical synthesiswas developed to convert glycerol into various value-added compounds. This study reports for the first time the use of Amberlyst-15 as a reaction mediumand redox catalyst for electrochemical conversion of glycerol. In the first part, the electrochemical performance of Amberlyst-15 over platinum (Pt)electrode was compared with that of conventional acidic (H2SO4) and alkaline (NaOH) media. Other parameters such as reaction temperature [room temperature (27°C) to 80 °C] and applied current (1.0 A to 3.0 A) were also examined. Under the optimized experimental condition, this novel electrocatalytic method successfully converted glycerol into glycolic acid after 8 h of electrolysis, with a yield of 45% and selectivity of 65%, as well as to glyceric acid after 3 h of electrolysis, with a yield of 27% and selectivity of 38%. In the second part of this study, two types of cathode electrodes, namely, activated carbon composite(ACC) and carbon black diamond (CBD) electrodes, were used in electrochemical conversion of glycerol. To the best of our knowledge, electrochemical studies of glycerol conversion using these electrodes have not been reported yet. Glycerol was also successfully reduced to lactic acid, 1,2-PDO, and 1,3-PDO, in addition to oxidation compounds (e.g. glycolic acid). Three operating parameters, namely, catalyst amount (6.4% to 12.8% w/v), reaction temperature [room temperature (27 °C) to 80 °C], and applied current (1.0 A to 3.0 A), were tested. In the presence of 9.6% w/v Amberlyst-15 at 2.0 A and 80 °C, the selectivity of glycolic acid can reach 72% and 68% (with yield of 66% and 58%) for ACC and CBD electrodes, respectively. Lactic acid was obtained as the second largest compound, withselectivity of 16% and yield of 15% for the ACC electrode and 27% selectivity and 21% yield for the CBD electrode. Finally, electro-oxidation and electroreduction of glycerol were performed in a two-compartment cell separated by a cation exchange membrane (Nafion 117). This study only focused on the electroreduction region. Three cathode electrodes (Pt, ACC, and CBD) were evaluated under the following conditions: 2.0 A, 80 °C, and 9.6% w/v Amberlyst-15. ACC demonstrated excellent performance in the electroreduction study and successfully reduced glycerol to 1,2-PDO, with a high selectivity of 85%. The selectivity of 1,2-PDO on Pt and CBD was 61% and 68%, respectively. Acetol and diethylene glycol were also obtained. The reaction mechanisms underlying the formation of these products are then proposed.

As cianotoxinas, potencialmente prejudiciais à saúde dos homens e animais, são toxinas produzidas pelas cianobactérias e que podem estar presentes em reservatórios utilizados para captação de água para abastecimento, sobretudo em função do agravamento das condições sanitárias das bacias hidrográficas. Diante disso, torna-se fundamental que a água esteja adequada ao consumo humano em sua distribuição. Uma das formas de tratamento para remoção das cianotoxinas que vem sendo estudada é por meio do uso de carvão ativado granular &#40;CAG&#41;, cuja eficiência depende de suas características intrínsecas e das condições operacionais. Outra possibilidade para remoção de tais toxinas se dá por meio da utilização de microrganismos capazes de promover sua biodegradação. A presente pesquisa analisou o potencial de remoção de microcistina por meio de adsorção por três diferentes CAGs comerciais &#40;materiais de origem: casca de coco, mineral e osso&#41; e por meio da degradação biológica por dois gêneros de bactérias. Para isso, foi utilizado um extrato de toxina produzido por meio do cultivo de Microcystis aeruginosa &#40;cepa BB005&#41; em meio WC, ao longo de 30 dias, com fotoperíodo de 12 h. Os carvões foram caracterizados de acordo com a massa específica aparente, umidade, pH, teor de cinzas, número de iodo, índice de azul de metileno e área superficial específica. Em seguida, foram realizados ensaios de adsorção com a microcistina &#40;concentração inicial de 100 &#181;g.L-1&#41; para construção de isotermas com tempo de equilíbrio de 1 h. As análises de toxina foram realizadas pelo método ELISA e os dados foram ajustados aos modelos matemáticos de Langmuir e de Freundlich. Os melhores resultados de adsorção foram obtidos a partir do carvão de origem mineral &#40;99&#37; de remoção&#41;, que apresentou valores maiores para número de iodo &#40;710 mgI2.g-1&#41;, índice de azul de metileno &#40;169 mL.g-1&#41;, área superficial específica &#40;911 m2.g-1&#41; e porcentagem de microporos &#40;70&#37;&#41;, com melhor ajuste da isoterma obtido pelo modelo de Freundlich &#40;R2 &#61; 0,88&#41;. Os ensaios de biodegradação da microcistina com os gêneros Sphingomonas sp. e Brevundimonas sp foram realizados com a toxina esterilizada e não esterilizada &#40;concentração inicial de 75 &#181;g.L-1&#41;. Os resultados demonstraram que tais bactérias não foram capazes de degradar a toxina esterilizada. Entretanto, foi observada degradação nos ensaios em que a toxina não estava esterilizada &#40;porcentagem de remoção de 98&#37;&#41;, indicando a presença de algum microrganismo e/ou enzima atuante nesse processo, uma vez que o cultivo da cepa para obtenção do extrato não foi realizado sob condições de assepsia. Recomenda-se, para futuras pesquisas, a identificação do responsável pela biodegradação da microcistina, bem como a aplicação do carvão mineral em maior escala &#40;filtro de leito fixo&#41;. Deste modo, será possível avaliar a formação de biofilme no leito de carvão, e comparar o desempenho da adsorção e da biodegradação na remoção do poluente-alvo em escala mais próxima à real. / The cyanotoxins, which are potentially harmful to the health of humans and animals, are toxins produced by cyanobacteria. They can be found in reservoirs used for water supply, especially due to the degradation of sanitary conditions within the watersheds. Therefore, it is essential to assure potable water for human consumption in its distribution. The use of granular activated carbon &#40;GAC&#41; has been studied for advanced water treatment and cyanotoxins\' removal. The efficiency of such technology depends on activated carbon intrinsic characteristics and operating conditions. Removing such toxins through biodegration by microrganisms is another possibility. The present study was perfomed in laboratory conditions and analyzed microcystin removal by adsorption by three commercial GACs &#40;source materials: coconut shell, mineral and bone&#41; and through the biological degradation by two genera of bacteria. An extract of toxin was produced by the cultivation of Microcystis aeruginosa &#40;strain BB005&#41;, in medium WC throughout 30 days, with a 12 h photoperiod. The activated carbon samples were characterized regarding the apparent density, moisture, pH, ash content, iodine number, methylene blue index and specific surface area. Thereafter, adsorption experiments were conducted with microcystin &#40;initial concentration of 100 &#181;g.L-1&#41; for estimating isotherms considering an equilibrium time of 1 h. The toxin analyses were performed by the ELISA &#40;Enzyme-Linked Immunosorbent Assay&#41; and the data were adjusted to the mathematical models of Langmuir and Freundlich. The best adsorption results were obtained with the mineral carbon &#40;removal percentages of 98&#37;&#41;, which also showed the highest values for the iodine number &#40;710 mgI2.g-1&#41;, methylene blue index &#40;169 mL.g-1&#41;, specific surface area &#40;911 m2.g-1&#41; and percentage of micropores &#40;70%&#41;, with best adjustment of the isotherm through the Freundlich model &#40;R2 &#61; 0.88&#41;. The biodegradation tests of microcystin with Sphingomonas sp. and Brevundimonas sp. were carried out with the sterile and non-sterile toxin &#40;initial concentration of 75 &#181;g.L-1&#41;. The results showed that these bacteria were not able to promote degradation of the toxin when it was sterilized. However, the degradation was observed in those tests in which the toxin was not sterilized &#40;reduction up to 98%&#41;, suggesting the presence of a microrganism and&#47;or an enzyme responsible for this process, since the cultivation of the strain for obtaining the extract was not performed under sterile conditions. As for future research, it is recommendedthe identification of the factor responsible for the biodegradation of the microcystin, as well as the study of the use of the activated carbon from mineral source in a larger scale &#40;fixed-bed filter&#41;. This would help to reach a scale closer to the real water treatment plants and evaluate the biofilm formation in the carbon bed, allowing the comparison of the performance of both adsorption and biodegradation processes in the removal of the target pollutant.

A expansão agrícola e a urbanização têm agravado a eutrofização artificial dos mananciais superficiais, devido ao aumento de seus níveis de nutrientes, como nitrogênio e fósforo. Nesses episódios, o crescimento excessivo de cianobactérias de elevada capacidade adaptativa e potencial de produção de cianotoxinas pode prejudicar homens e animais. As microcistinas estão entre as cianotoxinas mais encontradas em florações de cianobactérias tóxicas, de difícil remoção pelas tecnologias convencionais de Estações de Tratamento de Água (ETA). Como barreira adicional no tratamento avançado de águas de abastecimento, destaca-se o processo de adsorção com carvão ativado pulverizado (CAP) ou granular (CAG). Esta pesquisa avaliou a eficiência de remoção de microcistina-LR (MC-LR) por oito carvões ativados (7 CAGs e 1 CAP) produzidos a partir de matérias-primas diversificadas. Os carvões foram caracterizados quanto a umidade, teor de cinzas, pH, massa específica aparente, número de iodo, índice de azul de Metileno, coeficiente de desuniformidade, área superficial específica, volume de micro e mesoporos, análise elementar por Espectroscopia de Energia Dispersiva e fotomicrografia por Microscopia Eletrônica de Varredura. Avaliou-se a capacidade adsortiva dos carvões sobre a MC-LR por isotermas descritas pelos modelos matemáticos de Langmuir e Freundlich. Para tais ensaios, foram utilizadas amostras trituradas de carvão. Além disso, foram operadas quatorze colunas CAG em escala de bancada, de modo intermitente, com concentração inicial (Co) de MC-LR na faixa de 69 a 137 &#181;g/L. A concentração de toxina foi estimada pelo método ELISA (Ensaio de Imunoadsorção Enzimática). Os resultados indicaram que as propriedades do CA são influenciadas por seu material de origem e também pelo seu modo de produção, e que tais propriedades têm reflexo direto sobre a eficiência de remoção de MC-LR. Nos ensaios de adsorção de MC-LR com as amostras trituradas, os dados se ajustaram melhor ao modelo de Langmuir. O carvão à base de linhito (CGLIN), em dosagem de 100,0 mg/L e com 4h de tempo de contato, apresentou a maior capacidade de remoção (97,2%) de MC-LR (Co: 115,1 &#181;g/L), com qe,máx de 10,6 mg/g. O bom desempenho do CGLIN foi associado ao seu maior volume de mesoporos (0,53 cm3/g). Correlação significativa foi observada entre volume de mesoporos e qe,máx (r = 0,98, Pearson), o que foi corroborado pela Análise de Componentes Principais. Nos ensaios nas colunas de CAG, o carvão de hulha, CGHU (Co: 85 g/L) apresentou o melhor desempenho, seguido pelo carvão de casca de coco, CGCO4 (Co: 137 &#181;g/L), ambos com remoção média de MC-LR de 99,5%. Nos ensaios com as amostras trituradas, nenhuma das dosagens removeu MC-LR a concentrações menores que 1,0 &#181;g/L &#8211; valor máximo permitido pela Portaria MS nº 2.914/11 para água potável &#8211; enquanto que no início do tratamento com as colunas de CAG, com exceção do carvão de coco CGCO1, o efluente das demais amostras foi compatível com este limite. A divergência de resultados entre os dois tipos de ensaios indica que os experimentos com amostras de CAG trituradas podem alterar sua capacidade adsortiva e induzir a uma escolha incorreta do carvão mais adequado. Com isso, os resultados oferecem subsídios para o entendimento do desempenho das CAs sobre a remoção de cianotoxinas, amparando a aplicação do processo de adsorção em ETAs para minimização da incidência de intoxicações por água contaminada. / The agricultural expansion and urbanization has aggravated the artificial eutrophication of surface water sources, due to the increase of nutrient levels, such as nitrogen and phosphorus. In these episodes, the excessive growth of cyanobacteria of high adaptive capacity and potential to produce cyanotoxins can harm humans and animals. Microcystins are among the cyanotoxins most found in toxic cyanobacteria blooms, difficult to remove by conventional technologies of Water Treatment Plants (WTP). As an additional barrier in the advanced water treatment, the adsorption process with pulverized (PAC) or granular activated carbon (GAC) is highlighted. This research evaluated the efficiency of microcystin-LR (MC-LR) removal by eight activated carbons (7 GACs and 1 PAC) produced from diversified raw materials. The carbons were characterized by moisture, ash content, pH, bulk density, iodine number, Methylene blue index, desuniformity coefficient, specific surface area, micro and mesopore volume, elemental analysis by Energy Dispersive X-Ray Detector and photomicrography by Scanning Electron Microscopy. The MC-LR adsorptive capacity of the carbons was evaluated by isotherms that follow the mathematical models of Langmuir and Freundlich. For these tests, carbon crushed samples were used. Besides that, fourteen GAC columns were operated on bench scale, intermittently, with initial concentration (Co) of MC-LR in the range of 69 to 137 &#181;g/L. The toxin concentration was measured by ELISA (Enzyme-Linked Immunosorbent Assay). The results indicate that the AC properties are influenced by their source material and also by their production mode, and these properties have a direct effect on the efficiency of MC-LR removal. In the adsorption tests of MC-LR with the AC crushed samples, the data were better fitted to the Langmuir model. The lignite-based carbon (CGLIN), at a dosage of 100.0 mg/L and 4h of contact time, presented the highest MC-LR (Co: 115.1 &#181;g/L) removal capacity (97.2%), with a qe,máx of 10.6 mg/g. The good performance of CGLIN was associated with its higher volume of mesopores (0.53 cm3/g). Significant correlation was observed between volume of mesopores and qe,max (r = 0.98, Pearson), which was corroborated by Principal Component Analysis. In the GAC columns tests, the coal CGHU (Co: 85 &#181;g/L) presented the best performance, followed by the coconut carbon CGCO4 (Co: 137 &#181;g/L), both with MC-LR average removal from 99.5%. In the trials with the crushed samples, none of the dosages removed MC-LR at values less than 1.0 &#181;g/L &#8211; maximum permitted value by Portaria MS nº 2.914/11 for drinking water &#8211; while at the beginning of the treatment in the GAC columns, with the exception of the coconut carbon CGCO1, the effluent of the other samples was compatible with this limit. The divergence of results between these two types of assays indicates that the experiments with crushed samples may changes their adsorptive capacity and induce an incorrect choice of the most suitable AC. With this, the results provide support to understand the ACs performance on the cyanotoxins removal, supporting the application of the adsorption process in WTPs to minimize the incidence of poisoning by contaminated water.

O presente trabalho estuda a remoção dos fármacos amoxicilina (AMX), diclofenaco sódico (DCF) e paracetamol (PAR) em solução aquosa pelos processos de adsorção em batelada e coluna de leito fixo utilizando o carvão ativado granulado (CAG) como adsorvente. Os experimentos foram realizados para cada fármaco de forma independente. Na adsorção em batelada foram avaliadas as influências do pH (2 – 10), concentração de adsorvente (5 – 20 g L-1) e tempo de contato (5 – 350 min). Foi realizada a investigação da cinética de adsorção e também do equilíbrio de adsorção através de isotermas nas temperaturas de 25, 35 e 45 ºC. A adsorção em leito fixo foi estudada através de planejamentos experimentais, onde foram avaliados os efeitos da concentração inicial do poluente (C0: 20 – 100 mg L-1), massa do leito (W: 0,5 – 1,5 g) e vazão (Q: 3 – 5 mL min-1) sobre o tempo de saturação (tsat) e a quantidade adsorvida (qsat). Os modelos de Thomas, Bohart-Adams e Yan, além de um modelo desenvolvido no software EMSO foram utilizados para análise das curvas de ruptura. O CAG utilizado apresentou área BET de 463 m² g-1 e maior volume de microporos, de 0,20 cm³ g-1. Os experimentos em batelada mostraram que o pH não teve influência significativa sobre a remoção dos três fármacos. O equilíbrio de adsorção da AMX e do DCF foi atingido após 150 min e do PAR após 180 min. O modelo de PSO foi o que melhor representou a cinética de adsorção dos três fármacos. A isoterma de Langmuir descreveu o equilíbrio da AMX a 25 e 35 ºC, e o modelo de Sips a 45 ºC. Já a adsorção do DCF foi representada pela isoterma de Freundlich e o PAR pela de Redlich-Peterson. O estudo termodinâmico indicou que a adsorção dos três fármacos foi espontânea e favorável, além de aumentar com o aumento da temperatura. Na adsorção em leito fixo, foi observado menores valores de tsat com o aumento de C0 e de Q e diminuição de W. Foi verificado que qsat aumentou com o aumento de C0 e diminuição da Q para o planejamento do PAR, onde essa variável foi significativa. Já o aumento de W aumentou qsat no planejamento do PAR e diminuiu nos casos da AMX e DCF. A AMX foi o poluente que apresentou os menores tempos de saturação, seguido do DCF e do PAR, na adsorção em leito fixo. Foi constatado que o modelo de Yan foi o que melhor reproduziu o comportamento das curvas de ruptura para os três fármacos, na comparação com os outros modelos analíticos e com o modelo numérico proposto no software EMSO. De forma geral, foi verificado que os processos de adsorção tanto em batelada quanto em leito fixo apresentam potencial de aplicação como alternativa de tratamento avançado de água e efluentes que contenham fármacos. / The present work studies the removal of amoxicillin (AMX), sodium diclofenac (DCF), and paracetamol (PAR) from water by adsorption onto granular activated carbon in batch process and fixed bed column. Batch adsorption experiments were performed to evaluate the influence of pH (2 – 10), adsorbent concentration (5 – 20 g L-1) and contact time (5 – 350 min). Pseudo-first order, pseudo-second order and intraparticle diffusion models were evaluated in the kinetics investigation. Equilibrium adsorption was investigated using Langmuir, Freundlich, Sips and Redlich-Peterson equations. Fixed bed adsorption was studied through experimental design to evaluate initial contaminant concentration (C0, 20 – 100 mg L-1), amount of adsorbent (W, 0.5 – 1.5 g) and feed flow rate (Q, 3 – 5 mL min-1) effects. The analytical models of Thomas, Bohart-Adams and Yan were selected to investigate the breakthrough curves behavior. In addition, a numerical model was developed and solved using EMSO software. The granular activated carbon (GAC) used had BET surface area of 463 m² g-1 and volume of 0.20 cm³ g-1 of micropores. The pH had no significant effect on the adsorption removal of the three drugs. Adsorption equilibrium of AMX and DCF was reached after 150 min and 180 min for PAR. Pseudo second order model best represented kinetic adsorption of the three compounds. At best conditions in batch process, adsorbent concentration was 12.5 g L-1 for AMX and DCF and 10 g L-1 for PAR. Langmuir isotherm best described AMX adsorption equilibrium at 25 and 35 ºC, and Sips model at 45 ºC. DCF and PAR adsorption followed the Freundlich isotherm and Redlich-Peterson model, respectively. Thermodynamic study indicated that the three drugs adsorption were spontaneous and favorable processes. In addition, adsorption increased at higher temperatures. In fixed bed adsorption experiments, saturation time (tsat) decreased with the increase of initial concentration and flow rate for both drugs. W had positive effect on tsat. The amount adsorbed (qsat) was enhanced at higher C0 and lower Q. qsat was higher at higher Q for AMX and DCF and lower Q for PAR adsorption. Yan model best reproduced breakthrough curves behavior for all drugs among the analytical models and the numerical model developed on EMSO software. Thus, adsorption processes in batch mode and fixed bed column showed to be effective for the removal of drugs of different therapeutic classes from water.

A contaminação por metais pesados em corpos hídricos tem sido extensivamente tratada com motivo de grande preocupação sobretudo nos aspectos ambientais e efeitos para a saúde humana. Metais pesados apresentam respostas deletérias ao homem, sendo causa de intoxicações agudas e crônicas, além do desenvolvimento de doenças, para o meio ambiente a bioacumulação e os efeitos adversos as espécies podem criar o desequilíbrio ambiental de ecossistemas. As fontes de metais pesados em corpos d’águas, muita das vezes advém de esgotos domésticos e industriais, tratados ou não, de forma que os sistemas convencionais de tratamento de esgotos não são aptos a removerem os metais pesados de seus sistemas, assim sendo necessário outras tecnologias para sua remoção. São tecnologias utilizadas para a extração de metais pesados de efluentes os sistemas de adsorção, troca-iônica, filtração por membranas, extração líquido-líquido, e outros. A adsorção por carvão ativado é uma técnica eficiente de remoção de contaminantes orgânico e inorgânicos. Tendo em vista que a casca de arroz é um resíduo abundante é com amplo potencial de aplicação em diversos processos esta tem sido aplicado na produção de carvões ativados. Dessa forma, este trabalho investigou a eficiência da remoção de cobre em meio aquoso utilizando carvões ativados da casca de arroz. O processo de ativação por impregnação ácido e básica produziu carvões ativados com diferentes características químicas e respostas na extração de cobre em meio aquoso. Os ensaios para avaliação das variáveis independentes utilizaram do planejamento experimental por modelo fatorial. O carvão da casca de arroz ativado por hidróxido de potássio (CA-KOH) é um bom adsorvente de íons de cobre em solução com eficiências de remoção superiores a 96%. Enquanto a melhor condição para aplicação do carvão ativado por ácido fosfórico de casca de arroz (CA-H3PO4) ocorreu em pH de 7,3 por 65 minutos de tempo de contato com a remoção de 92,9% de cobre em solução. Foram estimados a partir do planejamento experimental os modelos de regressão para predição de extração de cobre, bem como suas superfícies de resposta. O CA-KOH apresentou alto potencial para aplicação em sistemas de tratamento de efluentes, sendo que a aplicação deste para atingir valores ótimos de extração deverá ocorrer em pH entre os intervalos inferior a 4 e superior 7 com o emprego de uma dosagem de 15-20 g de carvão/L de efluente. / The contamination by heavy metals in water bodies has been extensively treated because of great concern mainly on environmental aspects and effects on human health. Heavy metals present deleterious responses to humans, causing acute and chronic intoxications, besides the development of diseases, to the environment bioaccumulation and adverse effects species can create the environmental imbalance of ecosystems. Sources of heavy metals in bodies of water often come from domestic and industrial sewage, treated or untreated, so that conventional sewage treatment systems are not able to remove heavy metals from their systems, so it is necessary other technologies for its removal. The adsorption, ion exchange, membrane filtration, liquid-liquid extraction, and other technologies are used for the extraction of heavy metals from effluents. Activated carbon for adsorption is an efficient technique for removal of organic and inorganic contaminants. Considering that the rice husk is an abundant residue, it has a wide potential of application in several processes, this has been applied in the production of activated carbons. Thus, this work investigated the efficiency of the removal of copper in aqueous media using activated carbons of rice husk. The activation process by acid and basic impregnation produced activated carbons with different chemical characteristics and responses in copper extraction in aqueous medium. The trials for evaluation of the independent variables used experimental planning by factorial model. Potassium hydroxide-activated rice husk charcoal (CA-KOH) is a good solution of copper ions adsorbent with removal efficiencies greater than 96%. While the best condition for the application of activated carbon by phosphoric acid rice husk (CA-H3PO4) occurred in pH of 7.3 for 65 minutes of contact time with the removal of 92.9% copper solution. The regression models for copper extraction prediction, as well as their response surfaces, were estimated from the experimental design. The CA-KOH presented high potential for application in effluent treatment systems, and it is recommended to apply this in pH between the intervals below 4 and higher 7 using a dosage of 15-20 g of coal / L of effluent.

O processo de adsorção vem sendo utilizado como uma técnica eficaz para a remoção de íons metálicos em efluentes. Neste trabalho são apresentados os estudos para avaliar da capacidade de adsorção de cobalto em caulinita, um adsorvente de baixo custo, visando à remoção deste íon de soluções aquosas. Foi analisada a área superficial específica (S) em 25 amostras de materiais preparadas de diferentes modos: caulinita, bentonita e carvão ativado e, misturas de caulinita-bentonita e caulinita-carvão ativado. Estas misturas foram preparadas pela adição de 10, 20, 30, 40 e 50% de carvão ativado ou bentonita à caulinita. As amostras de caulinita-carvão ativado e caulinita in natura foram calcinadas a 600 e 1000 °C por 4 horas. Foi escolhida para os testes de adsorção a mistura de caulinita com 10% de carvão ativado por apresentar a melhor relação custo benefício em relação à S. Os parâmetros de adsorção investigados nesta mistura foram: tempo de contato, pH, concentração inicial de soluto, competição iônica e força iônica. Verificou-se que o tempo de contato e o pH otimizados para o propósito do trabalho foram 30 min e pH 6. Nestas condições a eficiência de remoção do íon cobalto da solução foi superior a 80%. Verificou-se que a presença de íons Cr e Zn, bem como o aumento da força iônica diminuem a capacidade de adsorção do Co na mistura adsorvente. As isotermas de Langmuir e Freundlich apresentaram R2 iguais a 0,906 e 0,597, respectivamente. Os parâmetros determinados nestas isotermas indicaram um processo espontâneo, ou seja, energeticamente favorável, para a adsorção do Co nas condições e que foram realizadas este trabalho. / The adsorption process has been used as an efficient technique for the removal of metallic ions in industrial effluent. In this work, it is presented the studies to evaluate the adsorption capacity of cobalt in kaolinite, a low cost adsorbent, aiming at the removal of this ion from aqueous solutions. The specific surface area (S) was analyzed in 25 samples prepared in different ways: kaolinite, bentonite and activated carbon and, mixtures of kaolinite-bentonite and kaolinite-activated carbon. These mixtures were prepared by adding to kaolinite 10, 20, 30, 40 or 50% of activated charcoal or bentonite. Samples of kaolinite-activated charcoal mixture and raw kaolinite were also calcined at 600 and 1000 °C for 4 hours. The adsorption parameters investigated for these adsorbents were: contact time, pH, solute initial concentration, ionic competition and ionic strength. It was found that the optimized contact time and pH, for the purpose of this work, were 30 min and pH 6. Under these conditions the cobalt ion removal efficiency was greater than 80%. It was verified that the presence of Cr and Zn ions, as well as the increase in ionic strength caused a decrease in the adsorption capacity of Co in the adsorbent mixture. The Langmuir and Freundlich isotherms presented R2 equal to 0.906 and 0.597, respectively. The parameters determined by these isotherms indicated a spontaneous process, i.e., energetically favorable, for the adsorption of Co under the conditions that this work was carried out.

Como os tratamentos convencionais de água e efluentes normalmente não reduzem as concentrações de pesticidas significativamente, torna-se necessário utilizar outros tipos de tratamento associados e uma alternativa é o pós-tratamento empregando carvão ativado (CA) para adsorção desses poluentes. Sua viabilidade econômica está associada ao seu reúso. O desenvolvimento de novas técnicas de regeneração de CA contaminado após uso, como o emprego de Processos Oxidativos Avançados (POA), tem recebido muita atenção. Os POA são caracterizados pela geração de radicais hidroxila (HOo), que são fortes oxidantes capazes de mineralizar uma vasta gama de substâncias, geralmente sem a necessidade de disposicão final. Nesse sentido, no presente trabalho estudou-se a aplicação dos POA baseados na peroxidação assistida por radiação ultravioleta (H2O2/UV) e oxidação promovida por peroximonossulfato de potássio (PMS) para regeneração de CA contaminado com o herbicida amicarbazona. Os processos estudados consistiram de duas etapas: adsorção, contactando-se a solução contendo o herbicida com o CA por um período pré-determinado; e tratamento, empregando os processos H2O2/UV ou PMS. Os resultados para o sistema H2O2/UV indicaram que não houve regeneração do CA, já que não se observou aumento na capacidade de adsorção após ciclos de regeneração consecutivos. Para o processo baseado em PMS, a regeneração é aparentemente efetiva. O tempo de regeneração, para uma razão oxidante/contaminante mais alta, mostrou-se importante no processo oxidativo PMS, já que maiores tempos de contato entre o oxidante e o carvão contaminado resultaram em uma melhora, mesmo que pequena, na capacidade do CA em adsorver a amicarbazona. / Conventional water and wastewater treatment processes usually do not significantly reduce the concentrations of pesticides, thus other types of treatment are necessary. An alternative is the use of activated carbon (AC) for the adsorption of these pollutants, although its economic viability is directly associated with its reuse. The development of new techniques for regenerating AC contaminated after usage, as the Advanced Oxidation Processes (AOP), have received much attention. AOP are characterized by the generation of hydroxyl radicals (HOo), which are strong oxidants able to mineralize a wide range of substances, often without the need for final disposal. Thus, the present study investigated the application of AOPs based on the ultraviolet-assisted peroxidation (H2O2/UV) and oxidation promoted by potassium peroxymonosulfate (PMS) for the regeneration of AC contaminated with the herbicide amicarbazone. The processes studied consisted of two steps: adsorption, by contacting the solution containing the herbicide with the AC for a certain period of time; and treatment, using the H2O2/UV or PMS processes. The results for the H2O2/UV system showed a maintenance of the AC´s adsorption capacity, since there was observed a constant adsorption capacity after consecutive regeneration cycles. For the PMSbased process, regeneration appears to be more effective with time exposure associated with higher oxidant/contaminant ratios, shown to be the most important factor in this case, since longer contact periods between the oxidant and the contaminated activated carbon resulted in an improvement, however small, in the ability of AC to adsorb amicarbazone.

Este trabalho visa avaliar o desenvolvimento microbiano e a capacidade de degradação de carbono orgânico total (COT) em quatro colunas adsorvedoras pósfiltração, em escala de bancada, em três ensaios em batelada: o primeiro de longa duração (84 dias) com afluente de água filtrada clorada com baixa concentração de COT (1,4 mg/L); o segundo de longa duração (84 dias) com afluente de solução de glicose e água filtrada clorada com concentração de COT de 6,0 mg/L e o terceiro de curta duração (21 dias) e com o mesmo afluente utilizado no segundo teste. Foi utilizado carvão ativado granular (CAG) de mesmas características nas colunas adsorvedoras, exceto as faixas de diâmetros dos grânulos, que variaram de 0,5 a 0,71 mm (coluna 1A), de 0,84 a 1,0 mm (coluna 1B) e de 1,0 a 1,19 mm (coluna 1C) nas três colunas que tinham o diâmetro interno de 1,2 cm. A coluna 2, com diâmetro interno de 2,1 cm, recebeu CAG com grânulos na mesma faixa de diâmetros da coluna 1B (0,84 a 1,0 mm). As eficiências de remoção de COT no primeiro ensaio foram bem menores (46 a 74%) do que aquelas dos ensaios 2 (94 a 97%) e 3 (96 a 97%). Estes últimos apresentaram grande desenvolvimento da microbiota e elevadas eficiências de remoção de COT, devido ao co-metabolismo e biorregeneração nas colunas pela introdução da glicose. Nas três colunas de mesmo diâmetro, foi observado que quanto menor a faixa de diâmetros dos grânulos de CAG, maior foi o desenvolvimento da microbiota (expresso em contagens de bactérias heterotróficas); e nas colunas com mesma faixa de diâmetros de CAG e com diferentes diâmetros de coluna (1B e 2), o desenvolvimento da microbiota foi muito semelhante nos ensaios de longa duração. Com relação às eficiências de remoção de COT, não houve diferença significativa entre as quatro colunas nos ensaios de longa e curta duração com adição de glicose; no ensaio de longa duração sem adição de glicose as colunas 1A e 2 apresentaram melhores resultados em relação às demais e não há uma explicação clara para tal fato. / The major purpose of this experimental work was to evaluate the microbial development and the capabilities of degradation of Total Organic Carbon (TOC) of four post-filtration adsorption columns operated as batch reactors in three bench scale tests. The firs batch column testing was conducted by means of one long duration runs (84 days each) and the columns were fed with filtered, chlorinated water with low COT concentration (1.4 mg/L). The second batch column testing was conducted by means of one long duration runs (84 days each) and the columns were fed with a glucose and filtered chlorinated water solution (resulting TOC = 6.0 mg/L). The third batch column testing was conducted by means of one short duration runs (21 days each) and the columns were fed with the same solution of the second batch column testing. The same type of Granular Activated Carbon (GAC) was employed in all columns, except for the average granule diameter ranges. They were 0.5 to 0.71 mm (column 1A), 0.84 to 1.0 mm (column 1B), and 1.0 to 1.19 mm (column 1C), for the 12 mm diameter columns. The 21 mm diameter column 2 had CAG granules with the same size range of column 1B (0.84 to 1.0 mm). The TOC removal efficiencies in the first batch column testing were lower (46 to 74%) than 2 (94 to 97%) and 3 (96 to 97%) batch column testing. The lasts batch column testing led to high microbial growth and high TOC removal efficiencies due to cometabolism and bioregenation in the columns fed with a glucose. Regarding the three columns with the same diameter, it was observed that the lower the GAC granule size range, the higher the microbial growth rate (expressed as heterotrophic plate count); the columns with the same GAC size range but different column diameters (columns 1B and 2) the microbial growth rates were very similar with respect to the long period runs. With respect to the TOC removal efficiencies, there were no significant differences between the four columns in the long duration test runs and the short duration runs with glucose addition; in the long duration run without glucose addition, columns 1A and 2 were much more efficient at removing TOC than the other column; there is no clear explanation for it.