Avaliação de floculante natural à base de Moringa oleifera no tratamento de água produzida na indústria do petróleo: aplicação da técnica combinada floculação/flotação

The principal effluent in the oil industry is the produced water, which is commonly associated to the produced oil. It presents a pronounced volume of production and it can be reflected on the environment and society, if its discharge is unappropriated. Therefore, it is indispensable a valuable careful to establish and maintain its management. The traditional treatment of produced water, usualy includes both tecniques, flocculation and flotation. At flocculation processes, there are traditional floculant agents that aren’t well specified by tecnichal information tables and still expensive. As for the flotation process, it’s the step in which is possible to separate the suspended particles in the effluent. The dissolved air flotation (DAF) is a technique that has been consolidating economically and environmentally, presenting great reliability when compared with other processes. The DAF is presented as a process widely used in various fields of water and wastewater treatment around the globe. In this regard, this study was aimed to evaluate the potential of an alternative natural flocculant agent based on Moringa oleifera to reduce the amount of oil and grease (TOG) in produced water from the oil industry by the method of flocculation/DAF. the natural flocculant agent was evaluated by its efficacy, as well as its efficiency when compared with two commercial flocculant agents normally used by the petroleum industry. The experiments were conducted following an experimental design and the overall efficiencies for all flocculants were treated through statistical calculation based on the use of STATISTICA software version 10.0. Therefore, contour surfaces were obtained from the experimental design and were interpreted in terms of the response variable removal efficiency TOG (total oil and greases). The plan still allowed to obtain mathematical models for calculating the response variable in the studied conditions. Commercial flocculants showed similar behavior, with an average overall efficiency of 90% for oil removal, however it is the economical analysis the decisive factor to choose one of these flocculant agents to the process. The natural alternative flocculant agent based on Moringa oleifera showed lower separation efficiency than those of commercials one (average 70%), on the other hand this flocculant causes less environmental impacts and it´s less expensive

Aplicação de géis de goma guar no processo de clarificação de salmouras e águas produzidas

Produced water is considered the main effluent of the oil industry, due to their increased volume in mature fields and its varied composition. The oil and grease content (TOG) is the main parameter for the final disposal of produced water. In this context, it is of great significance to develop an alternative method based on guar gum gel for the treatment of synthetic produced water, and using as the differential a polymer having high hydrophilicity for clarifying waters contaminated with oil. Thus, this study aims to evaluate the efficiency of guar gum gels in the remotion of oil from produced water. Guar gum is a natural polymer that, under specific conditions, forms three-dimensional structures, with important physical and chemical properties. By crosslinking the polymer chains by borate ions in the presence of salts, the effect salting out occurs, reducing the solubility of the polymer gel in water. As a result, there is phase separation with the oil trapped in the collapsed gel. The TOG was quantified from the spectroscopy in the ultraviolet and visible region. The system was proven to be highly efficient in the removal of dispersed oil from water produced synthetically, reaching removal percentages above 90%.

Análise da biorremediação de compostos monoaromáticos em água através da pseudomonas aeruginosa

The monoaromatic compounds are toxic substances present in petroleum derivades and used broadly in the chemical and petrochemical industries. Those compounds are continuously released into the environment, contaminating the soil and water sources, leading to the possible unfeasibility of those hydrous resources due to their highly carcinogenic and mutagenic potentiality, since even in low concentrations, the BTEX may cause serious health issues. Therefore, it is extremely important to develop and search for new methodologies that assist and enable the treatment of BTEX-contaminated matrix. The bioremediation consists on the utilization of microbial groups capable of degrading hydrocarbons, promoting mineralization, or in other words, the permanent destruction of residues, eliminating the risks of future contaminations. This work investigated the biodegradation kinetics of water-soluble monoaromatic compounds (benzene, toluene and ethylbenzene), based on the evaluation of its consummation by the Pseudomonas aeruginosa bacteria, for concentrations varying from 40 to 200 mg/L. To do so, the performances of Monod kinetic model for microbial growth were evaluated and the material balance equations for a batch operation were discretized and numerically solved by the fourth order Runge-Kutta method. The kinetic parameters obtained using the method of least squares as statistical criteria were coherent when compared to those obtained from the literature. They also showed that, the microorganism has greater affinity for ethylbenzene. That way, it was possible to observe that Monod model can predict the experimental data for the individual biodegradation of the BTEX substrates and it can be applied to the optimization of the biodegradation processes of toxic compounds for different types of bioreactors and for different operational conditions.

Análise da biorremediação de compostos monoaromáticos em água através da pseudomonas aeruginosa

The monoaromatic compounds are toxic substances present in petroleum derivades and used broadly in the chemical and petrochemical industries. Those compounds are continuously released into the environment, contaminating the soil and water sources, leading to the possible unfeasibility of those hydrous resources due to their highly carcinogenic and mutagenic potentiality, since even in low concentrations, the BTEX may cause serious health issues. Therefore, it is extremely important to develop and search for new methodologies that assist and enable the treatment of BTEX-contaminated matrix. The bioremediation consists on the utilization of microbial groups capable of degrading hydrocarbons, promoting mineralization, or in other words, the permanent destruction of residues, eliminating the risks of future contaminations. This work investigated the biodegradation kinetics of water-soluble monoaromatic compounds (benzene, toluene and ethylbenzene), based on the evaluation of its consummation by the Pseudomonas aeruginosa bacteria, for concentrations varying from 40 to 200 mg/L. To do so, the performances of Monod kinetic model for microbial growth were evaluated and the material balance equations for a batch operation were discretized and numerically solved by the fourth order Runge-Kutta method. The kinetic parameters obtained using the method of least squares as statistical criteria were coherent when compared to those obtained from the literature. They also showed that, the microorganism has greater affinity for ethylbenzene. That way, it was possible to observe that Monod model can predict the experimental data for the individual biodegradation of the BTEX substrates and it can be applied to the optimization of the biodegradation processes of toxic compounds for different types of bioreactors and for different operational conditions.

Remoção de fenol de efluentes aquosos utilizando floculação iônica

Oil exploration is one of the most important industrial activities of modern society. Despite its derivatives present numerous applications in industrial processes, there are many undesirable by-products during this process, one of them is water separated from oil, called water production, it is constituted by pollutants difficult to degrade. In addition, the high volume of generated water makes its treatment a major problem for oil industries. Among the major contaminants of such effluents are phenol and its derivatives, substances of difficult natural degradation, which due their toxicity must be removed by a treatment process before its final disposal. In order to facilitate the removal of phenol in wastedwater from oil industry, it was developed an extraction system by ionic flocculation with surfactant. The ionic flocculation relies on the reaction of carboxylate surfactant and calcium íons, yielding in an insoluble surfactant that under stirring, aggregates forming floc capable of attracting the organic matter by adsorption. In this work was used base soap as ionic surfactant in the flocculation process and evaluated phenol removal efficiency in relation to the following parameters: surfactant concentration, phenol, calcium and electrolytes, stirring speed, contact time, temperature and pH. The flocculation of the surfactant occurred in the effluent (initial phenol concentration = 100 ppm) reaching 65% of phenol removal to concentrations of 1300 ppm and calcium of 1000 ppm, respectively, at T = 35 °C, pH = 9.7, stirring rate = 100 rpm and contact time of 5 minutes. The permanence of the flocs in an aqueous medium promotes desorption of the phenol from the flake surface to the solution, reaching 90% of desorption at a time of 150 minutes, and the study of desorption kinetics showed that Lagergren model of pseudo-first order was adequate to describe the phenol desorption. These results shows that the process may configure a new alternative of treatment in regard the removal of phenol of aqueous effluent of oil industry.

Remoção de fenol de efluentes aquosos utilizando floculação iônica

Oil exploration is one of the most important industrial activities of modern society. Despite its derivatives present numerous applications in industrial processes, there are many undesirable by-products during this process, one of them is water separated from oil, called water production, it is constituted by pollutants difficult to degrade. In addition, the high volume of generated water makes its treatment a major problem for oil industries. Among the major contaminants of such effluents are phenol and its derivatives, substances of difficult natural degradation, which due their toxicity must be removed by a treatment process before its final disposal. In order to facilitate the removal of phenol in wastedwater from oil industry, it was developed an extraction system by ionic flocculation with surfactant. The ionic flocculation relies on the reaction of carboxylate surfactant and calcium íons, yielding in an insoluble surfactant that under stirring, aggregates forming floc capable of attracting the organic matter by adsorption. In this work was used base soap as ionic surfactant in the flocculation process and evaluated phenol removal efficiency in relation to the following parameters: surfactant concentration, phenol, calcium and electrolytes, stirring speed, contact time, temperature and pH. The flocculation of the surfactant occurred in the effluent (initial phenol concentration = 100 ppm) reaching 65% of phenol removal to concentrations of 1300 ppm and calcium of 1000 ppm, respectively, at T = 35 °C, pH = 9.7, stirring rate = 100 rpm and contact time of 5 minutes. The permanence of the flocs in an aqueous medium promotes desorption of the phenol from the flake surface to the solution, reaching 90% of desorption at a time of 150 minutes, and the study of desorption kinetics showed that Lagergren model of pseudo-first order was adequate to describe the phenol desorption. These results shows that the process may configure a new alternative of treatment in regard the removal of phenol of aqueous effluent of oil industry.

Avaliação de desempenho de ETAR urbanas

Na ultima década, a necessidade da definição de objectivos de gestão por parte das entidades gestoras, e a correspondente necessidade de verificação do cumprimento dos objectivos estabelecidos, levaram à implementação de iniciativas para o estudo e desenvolvimento de metedologias no domínio de avaliação de desempenho dos serviços de saneamento. O presente trabalho tem como principal objectivo, a avaliação do desempenho das nove infraestruturas em exploração pela SIMLIS, SA, tendo-se seleccionado, para este efeito, doze indicadores de desempenho,distribuídos pelos domínios da qualidade da água tratada; da eficiência e fiabilidade da ETAR; da utilização de água, energia e materiais; e da gestão de subprodutos. Como aspectos da avaliação de desempenho foram seleccionados, a conformidade com a licença de descarga, a qualidade da água rejeitada no meio recetor, a eficiência global da ETAR, o consumo de energia, o consumo de reagentes, a utilização de águas residuais tratadas, a produção e valorização de lamas e a produção de biogás. Para o processo de avaliação de desempenho, definiu-se um período de análise de um ano, nomeadamente o ano de 2013, para o qual se estabeleceram metas para cada um dos indicadores a avaliar. Conclui-se que a avaliação de desempenho é uma ferramenta essencial à gestão, pois permitiu analisar, não só o desempenho global da entidade gestora, mas também, avaliar o desempenho individual de cada uma das infraestruturas. Foi ainda possível, em alguns casos, avaliar o desempenho das ETAR em função do tipo de processo de tratamento utilizado. O uso adequado desta ferramenta de avaliação de desempenho permitiu à SIMLIS, de uma forma mais eficiente, aplicar acções correctivas quando identificados problemas e optimizar recursos, sendo usada como ferramenta de apoio à decisão.

A inserção da educação ambiental não formal no processo de implantação de saneamento ambiental na comunidade rural Colonia Mergulhão, São José dos Pinhais - PR

One of the biggest environmental problems of the population is the lack of sewage treatment, especially in rural communities and low-income. The development of technologies for efficient, low-cost sanitation need to be developed to meet the disadvantaged people of this basic service. This work was the implementation proposal of a technology called constructed wetlands, also known as Wastewater Treatment Plant for Roots Zone - ETEZR. The objective was to develop a non- formal environmental education proposal for redevelopment, using outreach methods for residents and deployment of this technology ETEZR in the rural community of Cologne Grebe in Sao Jose dos Pinhais - PR. With technical support from the Paranaense Technical Assistance and Rural Extension Institute -EMATER and the Federal Technological University of Paraná - UTFPR, 5 ETEZR were deployed in the colony through three theoretical and practical workshops, which involved total 67 people from the community 5 technicians EMATER and 13 of the Municipal Town Hall. Após4 months of implementation were carried out two collections of raw wastewater and treated to analyze physical, chemical and biological parameters. The results evaluated by chemical parameters BOD, COD, phosphorus, ammonia nitrogen comparing raw and treated sewage, demonstrate that ETEZR are effective in the treatment of sewage. 5 Seasons minimum and maximum efficiency between the basic parameters analyzed were 52.2 to 95.5% for BOD; 47 to 94.5% for COD; 21.5 to 96% phosphorus; 30-98% for ammonia nitrogen. Oils and greases, and a series of solid also achieved a significant reduction in their values when comparing the raw sewage and treated sewage, and biological parameters evaluated by means of coliforms showed a reduction of 80 to 99%. With the implementation of environmental education process aimed sanitation was possible to evaluate the perception of the population to accept the environmental sanitation technology using the ETEZR, understand the needs and sanitation concepts for the community. This research evaluated the development of the methodology applied by the non-formal environmental education in order to provide subsidies for rural sanitation plan process for the municipality.

Associação de sistema biológico do tipo lodo ativado com reatores air lift e fotocatálise heterogênea com TiO2 para a remediação de efluente oriundo da produção industrial de TNT

Trinitrotoluene in the purification step (TNT) produced in industries, are carried out two washes at the end of the process. The first wash is done with vaporized water, which originates from the first effluent called yellow water, then the second washing with the use of sodium sulfite is performed (Na2SO3), generating a second effluent red water. This study aimed to study the individual effects, as well as the association of heterogeneous photocatalysis using TiO2 and biological treatment in air lift reactor using activated sludge (bacterial biomass) for the remediation of wastewater contaminated with nitroaromatic compounds in order to reduce toxicity and adjust the legal parameters according to regulatory agencies for disposal in waterways. The photocatalytic treatment was conducted by factorial design obtaining the best reaction conditions (pH 6.5 and concentration of TiO2 0.1 gL-1), with best results obtained at 360 minutes of reaction, reducing the absorbance 97.00%, 94.20% of the chemical oxygen demand (COD), 67.70% of total phenols, as well as a total reduction of observed peaks and assigned to nitroaromatic compounds by high-performance liquid chromatography. In the biological treatment, there was a 53.40% reduction in absorbance at 275 nm 10.00% 36.00% COD and total phenols in a short time (3 days), while for extended periods (48 days) there was an antagonistic influence on the results so that was the elevation of these parameters (COD and total phenols) instead of reducing. Chromatographic analysis confirmed the effectiveness of the biological degradation by reducing the peaks corresponding to compounds DNT and TNT. The Association of photocatalytic and biological treatments decreased results in the order of 91.10% absorbance, 70.26% of total phenols and 88.87% of COD. While the combination of biological and photocatalytic treatments generated relatively lower efficiencies, with 77.30% of absorbance reduction, 62.10% reduction of total phenols and a decrease of 87.00% of COD. In general, when comparing the chemical and biological processes in isolation, the photocatalytic treatment showed the best results. However, comparing the results of isolation and established associations, the association biological x photocatalysis showed more promising results in the treatment of red water effluent.

Avaliação do potencial da macrófita Pistia stratiotes na exposição de íon cromo (VI): biossorção e tolerância

The environmental pollution caused by industries has increased the concentration of pollutants in the environment, especially in water. Among the most diverse contaminants, there is the metals, who may or may not to be heavy/toxic, causing effluent of difficult treatment when in low concentrations. The search for alternative measures of wastewater effluent treatment has led to studies using phytoremediation technique through the various matrices (plant, fungi, bacteria) as means of polishing treatment to remove contaminants by means of biosorption/bioaccumulation. In order to use the phytoremediation technique for removing metals of the environmental, it have been performed bioassay with the macrophyte Pistia stratiotes. The bioassays were realized with healthy plants of P. stratiotes acclimatized in a greenhouse, at room temperature and lighting conditions during 28 days of cultivate. The cultivations were performed in glass vessels containing 1 L of the hydroponic solution with chromium (VI) in the potassium dichromate form with concentration range 0.10 to 4.90 mg L-1. The experiments were performed by Outlining Central Composite Rotational (OCCR), where the kinetics of bioaccumulation and chlorophyll a fluorescence were monitored in plants of P. stratiotes during cultivation. The collections of the samples and cultive solution were performed according to the OCCR. The chromium levels were measured in samples of P. stratiotes and the remaining solutions by the methodology of atomic absorption spectrometry by flame. The tolerance of P. stratiotes in relation to exposure to chromium (VI) was analyzed by parameters of physiological activity by means of chlorophyll a fluorescence, using the portable fluorometer PAM (Pulse Amplitude Modulation). The development of P. stratiots and their biomass were related to the time factor, while bioaccumulation capacities were strongly influenced by factors of time and chromium concentration (VI). The chlorophyll fluorescence parameters were affected by chromium and the exposure time at the bioassays. It was obtained an higher metal removal from the root in relation to the sheet, reaching a high rate of metal removal in solution. The experimental data removal kinetics were represented by kinetic models Irreversibly Langmuir, Reversible Langmuir, Pseudo-first Order and Pseudo-second Order, and the best fit for the culture solution was the Reversible Langmuir model with R² 0.993 and for the plant the best model was Pseudo-second order with R² 0.760.

Avaliação de Impacto Ambiental, Valorização do Efluente e dos Resíduos Sólidos da Indústria Corticeira

A preocupação com o meio ambiente, nomeadamente na descarga de águas residuais, consumo de água excessivo e produção de resíduos industriais, está cada vez mais presente no quotidiano. Devido a estas problemáticas, efetuou-se a avaliação de impacte ambiental (AIA) do processo produtivo das rolhas de cortiça naturais, tratamento das águas de cozedura da cortiça (estudo da possível reutilização do efluente tratado) e valorização de subprodutos – resíduo sólido (raspa de cortiça), sendo estes os objetivos propostos para a realização da presente dissertação. Na AIA, efetuada no decorrer das fases da Análise do Ciclo de Vida (ACV), foram selecionadas 8 categorias de impacte – aquecimento global, acidificação, dessecação, toxicidade e ecotoxicidade, eutrofização, consumo de recursos não renováveis e oxidação foto-química. A água de cozedura caracterizou-se por uma elevada carga poluente, apresentando elevada concentração de cor, Carência Química de Oxigénio (CQO), taninos e lenhina e Sólidos Suspensos Totais (SST). O processo de tratamento proposto consistiu num pré-tratamento por ultrafiltração (UF), com membranas de 30.000 e 20.000 MWCO, seguido de adsorção por carvão ativado (comercial e produzido a partir de raspa de cortiça). No tratamento por UF, utilizando uma membrana de 30.000 MWCO, foram obtidas percentagens de remoção para a primeira amostra de água de cozedura de 74,8 % para a cor, 33,1 % para a CQO e para a segunda amostra de 85,2 % para a cor e 41,8 % para a CQO. Posteriormente, apenas para a segunda amostra de água de cozedura e com uma membrana de 20.000 MWCO, as percentagens de remoção obtidas foram superiores, de 93% para a cor, 68,9 % para a CQO, 88,4 % para taninos e lenhina e 43,0 % para azoto total. No tratamento por adsorção com carvão ativado estudou-se o tempo de equilíbrio do carvão ativado comercial e do carvão ativado produzido a partir de aparas de cortiça, seguindo-se o estudo das isotérmicas de adsorção, no qual foram analisados os parâmetros da cor e CQO para cada solução. Os ajustes dos modelos teóricos aos pontos experimentais demonstraram que ambos os modelos (Langmuir e Freundlich) poderiam ser considerados, uma vez que apresentaram ajustes idênticos. Relativamente ao tratamento de adsorção em contínuo do permeado, obtido por UF com membrana de 20.000 MWCO, constatou-se que ambos os carvões ativados (comercial e produzido) não ficaram saturados, tendo em consideração os tempos de saturação estimados pela capacidade máxima de adsorção (determinada para a isotérmica de Langmuir) e as representações gráficas dos valores experimentais obtidos para cada ensaio. No ensaio de adsorção com carvão ativado comercial verificou-se que o efluente tratado poderia ser descarregado no meio hídrico ou reutilizado no processo industrial (considerando os parâmetros analisados), uma vez que até aos 11 minutos de ensaio a concentração da solução à saída foi de 111,50 mg/L O2, para a CQO, e incolor, numa diluição de 1:20. Em relação à adsorção em contínuo com carvão ativado produzido verificou-se no ensaio 4 que o efluente resultante apresentou uma concentração de CQO de 134,5 mg/L O2 e cor não visível, numa diluição de 1:20, ao fim de 1h22 min de ensaio. Assim, concluiu-se que os valores obtidos são inferiores aos valores limite de emissão (VLE) presentes no Decreto-Lei n.º 236/98 de 1 de Agosto. O carvão ativado produzido apresentou elevada área superficial específica, com 870 m2/g, comparativamente ao carvão comercial que foi de 661 m2/g. O processo de extração da suberina a partir de raspa de cortiça isenta de extraíveis, efetuado através da metanólise alcalina, apresentou percentagens de extração superiores aos restantes métodos. No processo efetuado em scale-up, por hidrólise alcalina, obteve-se uma extração de 3,76 % de suberina. A aplicação da suberina no couro demonstrou que esta cera apresenta enormes potencialidades, uma vez que a sua aplicação confere ao couro um aspeto sedoso, com mais brilho e um efeito de “pull-up”.

Tratamento eletroquímico de efluente proveniente de caixas separadoras de água e óleo de postos revendedores de combustíveis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Síntese, caracterização e avaliação da capacidade bactericida de copolímeros à base de 2-vinilpiridina funcionalizados

Neste trabalho, dois copolímeros à base de 2-vinilpiridina (2Vpy), estireno (Sty) e divinilbenzeno (DVB) foram sintetizados empregando a técnica de polimerização em suspensão aquosa via radical livre. Os copolímeros com diferentes características morfológicas foram preparados variando a composição da mistura diluente, constituída por tolueno e n-heptano, solventes solvatantes e não solvatantes para as cadeias poliméricas. A caracterização estrutural desses materiais foi feita através de medidas de área específica, volume de poros, diâmetro médio de poros e densidade aparente. Além disso, esses materiais foram avaliados por microscopia ótica e eletrônica de varredura, por espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e análise elementar. Os copolímeros Sty-DVB-2Vpy foram modificados quimicamente através de reação de quaternização das unidades de 2Vpy usando dois reagentes: iodeto de metila e acrilonitrila. A quaternização dos copolímeros Sty-DVB-2Vpy foi confirmada através de espectroscopia de infravermelho, pelo aparecimento das bandas de absorção características do íon peridíneo e do grupo nitrila e também pela análise do comportamento térmico. Os produtos dessas reações foram submetidos à avaliação da capacidade bactericida através do método de contagem em placas contra suspensão de Escherichia coli. O copolímero do tipo gel quaternizado com iodeto de metila apresentou a maior ação bactericida registrada, com eficiência até a concentração de 104 células/mL. Contudo, a maioria dos materiais quaternizados não apresentou ação biocida significativa. Com o objetivo de maximizar a atividade bactericida dos materiais preparados, os copolímeros quaternizados e não quaternizados foram impregnados com iodo por meio de duas metodologias: em solução e em fase vapor. O teor de iodo incorporado foi quantificado por análise gravimétrica. Foi possível observar que os copolímeros quaternizados e impregnados com iodo se mostraram mais eficientes como agentes bactericidas que os copolímeros não funcionalizados impregnados com iodo. De uma forma geral, foi possível perceber que a ação bactericida dos polímeros é fruto da associação entre as suas características de porosidade, o grau de quaternização alcançado e o teor de iodo incorporado. Para efeito de comparação foram feitos também ensaios bactericidas com uma resina comercial à base de Sty-DVB com grupo amônio quaternário, VP OC 1950. Os testes mostraram que a resina comercial não possui atividade bactericida. A impregnação de iodo a essa resina comercial forneceu um material com ação biocida semelhante à do copolímero do tipo gel, quaternizado com iodeto de metila e impregnado com iodo

Contribuições para a construção de políticas públicas direcionadas à redução do lixo marinho em enseadas urbanas: estudo de caso na microbacia contribuinte do Canal de São Francisco e da Enseada de Jurujuba Niterói/ RJ.

Fonte de riquezas supostamente inesgotáveis, os oceanos e as zonas costeiras há muito tempo servem de depósito para todo tipo de resíduo produzido pelo homem, desde águas residuais a todo tipo de resíduos sólidos descartados inadequadamente e que acabam por originar o lixo marinho. A Baía de Guanabara é um reflexo histórico dessas ações mal geridas em terra e que acabam refletidas em seu espelho dágua. O presente estudo procura fazer uma analise sobre as origens do lixo marinho na Enseada de Jurujuba, localizada na Baía de Guanabara, e seu principal canal de drenagem, o Canal de São Francisco (CSF), com ênfase ao descarte de resíduos nas comunidades localizadas a montante do canal. Apresenta também uma avaliação da experiência de projetos de intervenção e prevenção à geração do lixo marinho, com destaque a um projeto de coleta de lixo flutuante com uso de embarcação, bem como a iniciativa da Prefeitura de Niterói em um Projeto de Gestão Integrada de Resíduos no alto da bacia contribuinte ao CSF. O trabalho foi estruturado através de observações de campo, entrevistas, analise de relatórios dos projetos envolvidos, bem como consulta a sites e blogs relacionados ao assunto. O fato de resíduos sólidos terminarem em um corpo hídrico torna sua retirada e destinação adequadas muito mais complicadas do que em terra, evidenciando a complexidade do lixo marinho. Os resultados apontam para a necessidade de mais estudos nas áreas periféricas, que abrangem a maior parte da população, com vista à integração de politicas públicas no planejamento de ações por bacias ou microbacias hidrográficas e como forma de prevenção à geração do lixo marinho e melhora da qualidade de vida dessas populações.

Mercury (II) removal from aqueous solutions by microporous materials

O Mercúrio é um dos metais pesados mais tóxicos existentes no meio ambiente, é persistente e caracteriza-se por bioamplificar e bioacumular ao longo da cadeia trófica. A poluição com mercúrio é um problema à escala global devido à combinação de emissões naturais e emissões antropogénicas, o que obriga a políticas ambientais mais restritivas sobre a descarga de metais pesados. Consequentemente o desenvolvimento de novos e eficientes materiais e de novas tecnologias para remover mercúrio de efluentes é necessário e urgente. Neste contexto, alguns materiais microporosos provenientes de duas famílias, titanossilicatos e zirconossilicatos, foram investigados com o objectivo de avaliar a sua capacidade para remover iões Hg2+ de soluções aquosas. De um modo geral, quase todos os materiais estudados apresentaram elevadas percentagens de remoção, confirmando que são bons permutadores iónicos e que têm capacidade para serem utilizados como agentes descontaminantes. O titanossilicato ETS-4 foi o material mais estudado devido à sua elevada eficiência de remoção (>98%), aliada à pequena quantidade de massa necessária para atingir essa elevada percentagem de remoção. Com apenas 4 mg⋅dm-3 de ETS-4 foi possível tratar uma solução com uma concentração igual ao valor máximo admissível para descargas de efluentes em cursos de água (50 μg⋅dm-3) e obter água com qualidade para consumo humano (<1.0 μg⋅dm-3), de acordo com a legislação Portuguesa (DL 236/98). Tal como para outros adsorbentes, a capacidade de remoção de Hg2+ do ETS- 4 depende de várias condições experimentais, tais como o tempo de contacto, a massa, a concentração inicial de mercúrio, o pH e a temperatura. Do ponto de vista industrial as condições óptimas para a aplicação do ETS-4 são bastante atractivas, uma vez que não requerem grandes quantidades de material e o tratamento da solução pode ser feito à temperatura ambiente. A aplicação do ETS-4 torna-se ainda mais interessante no caso de efluentes hospitalares, de processos de electro-deposição com níquel, metalúrgica, extracção de minérios, especialmente ouro, e indústrias de fabrico de cloro e soda cáustica, uma vez que estes efluentes apresentam valores de pH semelhantes ao valor de pH óptimo para a aplicação do ETS-4. A cinética do processo de troca iónica é bem descrita pelo modelo Nernst-Planck, enquanto que os dados de equilíbrio são bem ajustados pelas isotérmicas de Langmuir e de Freundlich. Os parâmetros termodinâmicos, ΔG° and ΔH° indicam que a remoção de Hg2+ pelo ETS-4 é um processo espontâneo e exotérmico. A elevada eficiência do ETS-4 é confirmada pelos valores da capacidade de remoção de outros materiais para os iões Hg2+, descritos na literatura. A utilização de coluna de ETS-4 preparada no nosso laboratório, para a remoção em contínuo de Hg2+ confirma que este material apresenta um grande potencial para ser utilizado no tratamento de águas. ABSTRACT: Mercury is one of the most toxic heavy metals, exhibiting a persistent character in the environment and biota as well as bioamplification and bioaccumulation along the food chain. Natural inputs combined with the global anthropogenic sources make mercury pollution a planetary-scale problem, and strict environmental policies on metal discharges have been enforced. The development of efficient new materials and clean-up technologies for removing mercury from effluents is, thus, timely. In this context, in my study, several microporous materials from two families, titanosilicates and zirconosilicates were investigated in order to assess their Hg2+ sorption capacity and removal efficiency, under different operating conditions. In general, almost all microporous materials studied exhibited high removal efficiencies, confirming that they are good ion exchangers and have potential to be used as Hg2+ decontaminant agents. Titanosilicate ETS-4 was the material most studied here, by its highest removal efficiency (>98%) and lowest mass necessary to attain it. Moreover, according with the Portuguese legislation (DL 236/98) it is possible to attain drinking water quality (i.e. [Hg2+]< 1.0 μg⋅dm-3) by treating a solution with a Hg2+ concentration equal to the maximum value admissible for effluents discharges into water bodies (50 μg⋅dm-3), using only 4 mg⋅dm-3 of ETS-4. Even in the presence of major freshwater cations, ETS-4 removal efficiency remains high. Like for other adsorbents, the sorption capacity of ETS-4 for Hg2+ ions is strongly dependent on the operating conditions, such as contact time, mass, initial Hg2+ concentration and solution pH and, to a lesser extent, temperature. The optimum operating conditions found for ETS-4 are very attractive from the industrial point of view because the application of ETS-4 for the treatment of wastewater and/or industrial effluents will not require larges amounts of adsorbent, neither energy supply for temperature adjustments becoming the removal process economically competitive. These conditions become even more interesting in the case of medical institutions liquid, nickel electroplating process, copper smelter, gold ore tailings and chlor-alkali effluents, since no significant pH adjustments to the effluent are necessary. The ion exchange kinetics of Hg2+ uptake is successfully described by the Nernst-Planck based model, while the ion exchange equilibrium is well fitted by both Langmuir and Freundlich isotherms. Moreover, the feasibility of the removal process was confirmed by the thermodynamic parameters (ΔG° and ΔH°) which indicate that the Hg2+ sorption by ETS-4 is spontaneous and exothermic. The higher efficiency of ETS-4 for Hg2+ ions is corroborate by the values reported in literature for the sorption capacity of other adsorbents for Hg2+ ions. The use of an ETS-4 fixed-bed ion exchange column, manufactured in our laboratory, in the continuous removal of Hg2+ ions from solutions confirms that this titanosilicate has potential to be used in industrial water treatment.