The Chlorine-Ammonia Process was developed recently as a preoxidation process to minimize the formation of bromate during ozonation of the waters containing a significant bromide concentration. Chlorine is added first, followed by ammonia 5-10 minutes later, with the goal of sequestering bromide in monobromamine before the subsequent ozonation step. The goal of this research was to improve the Chlorine-Ammonia Process by introducing a very short prechlorination step (i.e., 30 seconds before addition of ammonia) to minimize overall disinfection by-product formation. Also, in this strategy, formation of a powerful halogenating agent, HOBr, is minimized and bromochloramine (NHBrCl) is used predominantly instead of monobromamine to sequester bromide during ozonation. To support this improved approach to bromide sequestration, this study examined the formation and decay of bromochloramine as a function of operating conditions, such as pH and Cl2/N ratio, and refined a chemical kinetic model to predict haloamine concentrations over time. Two natural organic matter (NOM) sources were used in this study (Lake Austin, Texas and Claremore Lake, Oklahoma) to study the effect of NOM on monochloramine and total chlorine decay after 30 seconds of prechlorination. The rate of the reaction between haloamines and fast and slow sites on the NOM was estimated. A kinetics model was developed to model total chlorine decay after a short prechlorination time. The model is based on the Unified Haloamine Kinetic Model developed by Pope (2006). Pope`s model failed to model the initial monochloramine concentration after 30 seconds prechlorination time as well as the monochloramine and total chlorine decay over time. The modified model shows an excellent prediction of monochloramine and total chlorine decay after 30 seconds prechlorination time at pH range of 6.5-8.0 and over a carbonate buffer concentration range of 2-10 mM. The model includes a new bromochloramine decay scheme via the reaction with monochloramine and with itself. In addition, new rate constants for the reaction of HOCl with bromide ion and reaction of HOBr with monochloramine were added. The hypobromous acid formation rate was found to be an acid-catalyzed reaction, which confirms the finding of Kumar et al. (1987). A new value of the acid catalysis effect of hydrogen ion was estimated. New terms were introduced to the hyprobromous acid formation rate including the acid catalysis effect of bicarbonate, carbonic acid, and ammonium ion. In addition, the reaction of HOBr with monochloramine to form bromochloramine was found to be an acid-catalyzed reaction, and a new value of the rate constant was estimated. / text

O crescimento desordenado das cidades, a utilização de áreas para plantio próximas aos mananciais e o lançamento de águas residuárias domésticas e industriais sem tratamento são consideradas as principais fontes de poluição dos corpos d´água. Tal poluição contribui para o enriquecimento dos corpos hídricos em relação aos nutrientes. Isto, combinado com fatores climáticos proporciona condições para a ocorrência de florações de algas que podem apresentar espécies potencialmente tóxicas. Desta forma, aumenta a preocupação com desenvolvimento de técnicas de tratamento que forneçam água de qualidade garantindo a saúde da população consumidora. Nesta pesquisa, foram preparadas águas de estudo com diferentes concentrações de microcistina, com as quais foram testados alguns processos de tratamento, em escala de bancada, que consistiram na pré-cloração, adsorção em carvão ativado em pó, coagulação/floculação, flotação por ar dissolvido e centrifugação. O fluxograma de tratamento com aplicação de carvão ativado logo após a mistura rápida foi o que apresentou melhores resultados em termos de cor aparente, turbidez e concentração residual de microcistina. Foi avaliada a influência da concentração de microcistina nos tratamentos simulados. Constatou-se que para 104,92 µg/L de microcistina a aplicação de 3,0 mg\'CL IND.2\'/L (10 segundos antes da mistura rápida) e 30 mg/L de CAP (logo após a mistura rápida) não foram capazes de reduzir a concentração de microcistina para menos de 1 µg/L, conforme o limite estabelecido pela Portaria 518/04 do Ministério da Saúde. Assim, optou-se pela estimativa da dosagem mínima de carvão ativado em pó (CAP) em função da concentração inicial de microcistina das três águas preparadas. O residual de microcistina em cada água preparada, após a aplicação da dosagem estimada de CAP, foi: Água de Estudo 1 = 0,80 µg/L, Água de Estudo 2 = 0,82 µg/L e Água de Estudo 3 = 0,23 µg/L. / The disordered growth of cities, the use of planting areas near the water sources and the launch of domestic and industrial wastewater without treatment are the main sources of water bodies\' pollution. Such pollution contributes to increase the nutrient loading in the water bodies. In association with climatic factors, this enrichment of nutrient provides suitable conditions for the bloom of potentially toxic algae. Thus, increases the concern over to develop treatment techniques that provide water quality able to ensure the health of the consumer population. In this research, waters were prepared with different concentrations of microcystin and some treatments were tested in bench scale. These tests consisted in prechlorination, adsorption on powdered activated carbon, coagulation/flocculation, dissolved air flotation and centrifugation. The diagram of treatment with activated carbon application after the rapid mix showed better results of apparent color, turbidity and residual concentration of microcystin. The influence of the concentration of microcystin in the simulated treatments was evaluated. It was found that for 104.92 µg/L of microcystin the application of 3.0 mg\'CL IND.2\'/L (10 seconds before rapid mix) and 30 mg/L of PAC (after a quick mixture) were not able to reduce the concentration of microcystin to less than 1 µg/L, as the limit established by Order 518/04 of the Health Ministry. Thus, it was decided to estimate the minimum dosage of powdered activated carbon (PAC) according to the initial concentration of microcystin found in the three prepared waters. The residual concentration of microcystin in each water, after the estimated dosage application of PAC was: Water 1 = 0.80 µg/L; Water 2 = 0.82 µg/L; Water 3 = 0, 23 µg/L.

O crescimento desordenado das cidades, a utilização de áreas para plantio próximas aos mananciais e o lançamento de águas residuárias domésticas e industriais sem tratamento são consideradas as principais fontes de poluição dos corpos d´água. Tal poluição contribui para o enriquecimento dos corpos hídricos em relação aos nutrientes. Isto, combinado com fatores climáticos proporciona condições para a ocorrência de florações de algas que podem apresentar espécies potencialmente tóxicas. Desta forma, aumenta a preocupação com desenvolvimento de técnicas de tratamento que forneçam água de qualidade garantindo a saúde da população consumidora. Nesta pesquisa, foram preparadas águas de estudo com diferentes concentrações de microcistina, com as quais foram testados alguns processos de tratamento, em escala de bancada, que consistiram na pré-cloração, adsorção em carvão ativado em pó, coagulação/floculação, flotação por ar dissolvido e centrifugação. O fluxograma de tratamento com aplicação de carvão ativado logo após a mistura rápida foi o que apresentou melhores resultados em termos de cor aparente, turbidez e concentração residual de microcistina. Foi avaliada a influência da concentração de microcistina nos tratamentos simulados. Constatou-se que para 104,92 µg/L de microcistina a aplicação de 3,0 mg\'CL IND.2\'/L (10 segundos antes da mistura rápida) e 30 mg/L de CAP (logo após a mistura rápida) não foram capazes de reduzir a concentração de microcistina para menos de 1 µg/L, conforme o limite estabelecido pela Portaria 518/04 do Ministério da Saúde. Assim, optou-se pela estimativa da dosagem mínima de carvão ativado em pó (CAP) em função da concentração inicial de microcistina das três águas preparadas. O residual de microcistina em cada água preparada, após a aplicação da dosagem estimada de CAP, foi: Água de Estudo 1 = 0,80 µg/L, Água de Estudo 2 = 0,82 µg/L e Água de Estudo 3 = 0,23 µg/L. / The disordered growth of cities, the use of planting areas near the water sources and the launch of domestic and industrial wastewater without treatment are the main sources of water bodies\' pollution. Such pollution contributes to increase the nutrient loading in the water bodies. In association with climatic factors, this enrichment of nutrient provides suitable conditions for the bloom of potentially toxic algae. Thus, increases the concern over to develop treatment techniques that provide water quality able to ensure the health of the consumer population. In this research, waters were prepared with different concentrations of microcystin and some treatments were tested in bench scale. These tests consisted in prechlorination, adsorption on powdered activated carbon, coagulation/flocculation, dissolved air flotation and centrifugation. The diagram of treatment with activated carbon application after the rapid mix showed better results of apparent color, turbidity and residual concentration of microcystin. The influence of the concentration of microcystin in the simulated treatments was evaluated. It was found that for 104.92 µg/L of microcystin the application of 3.0 mg\'CL IND.2\'/L (10 seconds before rapid mix) and 30 mg/L of PAC (after a quick mixture) were not able to reduce the concentration of microcystin to less than 1 µg/L, as the limit established by Order 518/04 of the Health Ministry. Thus, it was decided to estimate the minimum dosage of powdered activated carbon (PAC) according to the initial concentration of microcystin found in the three prepared waters. The residual concentration of microcystin in each water, after the estimated dosage application of PAC was: Water 1 = 0.80 µg/L; Water 2 = 0.82 µg/L; Water 3 = 0, 23 µg/L.

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