Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, CAPES.

A identificação dos possíveis parâmetros determinantes da toxicidade em efluente industrial buscando a redução da carga poluidora auxilia na minimização dos efeitos tóxicos decorrentes do lançamento de efluente industrial em um corpo receptor de forma a preservar a biota aquática. O objetivo deste estudo foi adequar os parâmetros físicos e químicos e o fator de toxicidade à legislação ambiental.O estudo foi dividido em três etapas realizadas ao longo de outubro de 2010 a fevereiro de 2015. A Etapa 1 incluiu as análises físicas, químicas e toxicológicas de amostras coletadas no período entre outubro de 2010 e novembro de 2012, anterior às modificações realizadas na linha de tratamento superficial. A Etapa 2, realizada após alterações feitas na linha de tratamento, apresenta os resultados das análises físicas, químicas e toxicológicas feitas entre julho e setembro de 2013. A Etapa 3 mostra a caracterização física, química e toxicológica do efluente entre janeiro de 2014 e fevereiro de 2015, depois de executadas adequações no tratamento de efluentes. Entre as 14 amostras de efluente tratado analisadas, sete pertencem à Etapa 1 (Amostras 1 a 7); duas à Etapa 2 (Amostras 8 e 9) e cinco à Etapa 3 (Amostras 10 a 14). As análises físicas, químicas e toxicológicas foram efetuadas em laboratórios credenciados junto ao órgão ambiental. Considerando-se a natureza complexa dos efluentes industriais, a análise dos resultados obtidos revela melhoria na qualidade do efluente tratado com adequação à legislação vigente, em relação aos parâmetros físicos e químicos. A redução dos metais zinco, ferro e níquel teve êxito com a instalação do filtro prensa. O uso de carvão em pó possibilitou a adequação do parâmetro surfactante. Foi constatada, na Etapa 2, a adequação do efluente junto à CONSEMA 129/2006. A verificação do pH por meio de equipamento de medida, a partir da Etapa 3, não possibilita o ajuste deste parâmetro, mas permitiu o melhor controle do pH do efluente tratado. As modificações efetuadas permitiram a adequação do efluente ao padrão de lançamento quanto aos parâmetros físicos e químicos. No entanto, foi observado um aumento de toxicidade no efluente provavelmente devido ao mecanismo utilizado na redução dos surfactantes. Com base nestas informações, devem ser definidas outras estratégias e metas na tentativa de atender à legislação quanto à toxicidade antes do descarte no corpo receptor. / The identification of possible determinants of toxicity parameters in industrial effluent aiming the reduction of the pollutant load helps in minimizing the toxic effects of the dump of industrial effluents in a receiving body in order to preserver the aquatic biota. The aim of this study was to adapt the physicochemical parameters and the toxicity factor to the environmental legislation. The study was divided into three steps performed between October 2010 and February 2015. Step 1 included physical, chemical and toxicological samples collected between October 2010 and November 2012, before the changes performed in the plating process. The step 2, performed after the changes in the finishing treatment process, shows the physical, chemical and toxicological result of the analyses made between July and September 2013. Step 3 shows the physical, chemical and toxicological characterization of the effluent between January 2014 and February 2015, after performed adjustments in the effluent treatment. Among fourteen analysed samples of treated effluent, seven belonged to Step 1 (Samples 1 to 7); two to Step 2 (Samples 8 and 9) e five to Step 3 (Samples 10 to 14). The physical, chemical and toxicological analysis were made in laboratories accredited by the environmental agency. Considering the complex nature of industrial effluents, the analysis of the result shows the improvement in the quality of the treated effluent with the adequacy to the current legislation in relation to physicochemical parameters. The reduction of zinc, iron and nickel had success with the installation of the filter press. The use of powder coal was responsible for the adequacy of the effluent to CONSEMA 129/2006. The check of pH by measurement equipments, from Step 3, does not allow the adjustment of this parameter, but it allowed the better control of the pH on the treated effluent. The modifications performed allowed the adequacy of the effluent to the launch default in relation to the physicochemical parameters. However, it has been observed an increasing of toxicity in the effluent probably due to the mechanism for reducing the surfactants that it was used. Based in this information, other strategies should be defined in an attempt to comply with the legislation about the toxicity before the dump in the receiving body.

The process of precious metal refining can be up to 99.99% efficient at best, and although it may seem small, the amount of valuable metal lost to waste streams is appreciable enough to warrant recovery. The method currently used to remove entrained metal ions from refinery wastewaters, chemical precipitation, is not an effective means for selective recovery of precious metals from a wastewater. Biosorption, the ability of certain types of biomass to bind and concentrate metals from even very dilute aqueous solutions, may be an effective point-source metal recovery strategy. The yeast, Saccharomyces cerevisiae, has been found capable of sorbing numerous precious and base metals, and is a cheap and abundant source of biomass. As such, it represents a possible precious metal sorbent for application to refining wastewaters. In this investigation, S. cerevisiae biomass was immobilized, using polyethyleneimine and glutaraldehyde, to produce a suitable sorbent, which was found to be capable of high platinum uptake (150 to 170 mg/g) at low pH (< 2). The sorption mechanism was elucidated and found to be a chemical reaction, which made effective desorption impossible. The sorption process was investigated in a packed bed column conformation, the results of which showed that the diameter and height of the column require further optimization in order to attain the metal uptake values achieved in the batch studies. When applied to a refinery wastewater, two key wastewater characteristics limited the success of the sorption process; the high inorganic ion content and the complex speciation of the platinum ions. The results proved the concept principle of platinum recovery by immobilized yeast biosorption and indicated that a more detailed understanding of the platinum speciation within the wastewater is required before the biosorption process can be applied. Overall, the sorption of platinum by the S. cerevisiae sorbent was demonstrated to be highly effective in principle, but the complexity of the wastewater requires that pretreatment steps be taken before the successful application of this process to an industrial wastewater.

In an attempt to overcome the high maintenance and costs associated with traditional physico-chemical methods, much work is being done on the application of enzymes for the recovery of valuable metals from solutions and industrial effluents. One of the most widely studied enzymatic metal recovery systems uses hydrogenase enzymes, particularly from sulphate reducing bacteria (SRB). While it is known that hydrogenases from SRB mediate the reductive precipitation of metals, the mechanism of enzymatic reduction, however, is not yet fully understood. The main aim of the present study was to investigate the role of a hydrogenase enzyme in the removal of rhodium from both aqueous solution and industrial effluent. A quantitative analysis of the rate of removal of rhodium(III) by a resting SRB consortium under different initial rhodium and biomass concentrations, pH, temperature, presence and absence of SRB cells and electron donor, was studied. Rhodium speciation was found to be the main factor controlling the rate of removal of rhodium from solution. SRB cells were found to have a higher affinity for anionic rhodium species, as compared to both cationic and neutral species, which become abundant when speciation equilibrium was reached. Consequently, a pH-dependant rate of rhodium removal from solution was observed. The maximum SRB uptake capacity for rhodium was found to be 66 mg rhodium per g of resting SRB biomass. Electron microscopy studies revealed a time-dependant localization and distribution of rhodium precipitates, initially intracellularly and then extracellularly, suggesting the involvement of an enzymatic reductive precipitation process. A hydrogenase enzyme capable of reducing rhodium(III) from solution was isolated and purified by PEG, DEAE-Sephacel anion exchanger and Sephadex G200 gel exclusion. A distinct protein band with a molecular weight of 62kDa was obtained when the hydrogenase containing fractions were subjected to a 10% SDS-PAGE. Characterization studies indicated that the purified hydrogenase had an optimum pH and temperature of 8 and 40°C, respectively. A maximum of 88% of the initial rhodium in solution was removed when the purified hydrogenase was incubated under hydrogen. Due to the low pH of the industrial effluent (1.31), the enzymatic reduction of rhodium by the purified hydrogenase was greatly retarded. It was apparent that industrial effluent pretreatment was necessary before the application an enzymatic treatment method. In the present study, however, it has been established that SRB are good candidates for the enzymatic recovery of rhodium from both solution and effluent.

The continuing industrial development has led to a corresponding increase in the amount of waste water generation leading to a consequential decline in levels and quality of the natural water in the ecosystem. Textile industries consume over 7 x 10[superscript 5] tons of dyes annually and use up to 1 litre of water per kg of dye processed and are third largest polluters in the world, the problem being aggravated by the inefficiencies of the dye houses. An abundance of physio-chemical methods are in use world wide, however, there is increasing concern as to their impact in effectively treating textile effluents as they introduce secondary pollutants during the ‘remediation’ process which are quite costly to run, maintain and clean up. Research on biological treatment has offered simple and cost effective ways of bioremediating textile effluents. While aerobic treatment of textile dyes and their effluents has been reported, its major draw back is commercial up-scaling and as such anaerobic systems have been investigated and shown to degrade azo dyes, which form the bulk of the dyes used world wide. However, the mechanisms involved in the bioremediation of these dyes are poorly understood. The aims of this study were to identify and investigate the role of enzymes produced by sulphate reducing bacteria (SRB) in bioremediating textile dye and their effluents. Sulphate reducing bacteria were used in this study because they are tolerant to harsh environmental conditions and inhibit the proliferance of pathogenic micro-organisms. The appearance of clear zones in agar plates containing azo dye concentrations ranging from 10 – 100 mgl[superscript -1] showed the ability of SRB to decolourize dyes under anaerobic conditions. Assays of enzymes previously reported to decolourise azo dyes were not successful, but led to the identification of hydrogenase enzyme being produced by SRB. The enzyme was found to be localised in the membrane and cytoplasm. A surface response method was used to optimize the extraction of the enzyme from the bacterial cells resulting in approximately 3 fold increase in hydrogenase activity. Maximum hydrogenase activity was found to occur after six days in the absence of dyes but was found to occur after one day in the presence of azo dyes. A decline in hydrogenase activity thereafter, suggested inhibition of enzymatic activity by the putative aromatic amines produced after azo cleavage. Purification of the hydrogenase by freeze drying, poly ethylene glycol, and Sephacryl – 200 size exclusion- ion exchange chromatography revealed the enzyme to have a molecular weight of 38.5 kDa when analyzed by a 12 % SDS-PAGE. Characterisation of the enzyme revealed optimal activity at a pH of 7.5 and temperature of 40 °C while it exhibited a poor thermal stability with a half-life of 32 minutes. The kinetic parameters V[subscript max] and K[subscript m] were 21.18 U ml[superscript -1} and 4.57 mM respectively. Application of the cell free extract on commercial dyes was not successful, and only whole SRB cells resulted in decolourisation of the dyes. Consequently trials on the industrial dyes and effluents were carried out with whole cells. Decolourisation rates of up to 96 % were achieved for the commercial dyes and up to 93 % for the industrial dyes over a period of 10 days.

No abstract available. / Dissertation (MSc (Water Utilization))--University of Pretoria, 2006. / Chemical Engineering / unrestricted

The start-up and step-up operation of two 16-liter, continuously operated, upflow anaerobic reactors receiving baker's yeast wastewater is presented in this thesis. The two reactors (A and B) were almost identical in construction. Reactor A was a conventional upflow anaerobic sludge blanket (UASB) reactor, and reactor B was a hybrid reactor. In addition to all the features of a UASB reactor, a fixed-film structure was installed in the mid section of the reactor B. Both reactors were operated at 35 °C and at a constant hydraulic retention time of 7 days. The waste strength, expressed in chemical oxygen demand (COD), was varied from 8 g COD liter⁻¹ (during the start-up) to 58 g COD liter⁻¹. The organic loading rate ranged from 1.1 to 9.4 g COD liter⁻¹ day⁻¹. The start-up lasted for the first 46 days. Towards the end of the start-up, methane production rates of 0.23 and 0.28 liter CH₄ liter⁻¹ day⁻¹ and COD reductions of 62.2% and 67.2% were achieved at organic loading rates of 1.1 and 1.3 g COD liter⁻¹ day⁻¹ for reactors A and B respectively. During the step-up operation, maximum methane production rates were, for reactors A and B respectively, 0.91 and 0.95 liter CH₄ liter⁻¹ day⁻¹ at organic loading rates of 5.8 and 6.4 g COD liter⁻¹ day⁻¹. In addition, reactor profiles for sludge concentration, pH, volatile fatty acids, and COD are also presented. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Centro de Pesquisa e Desenvolvimento Leopoldo Américo Miguêz de Mello, CENPES.

Uma das principais fontes de poluição dos recursos hídricos são os efluentes líquidos industriais. Dentre esses, destacam-se os efluentes de refinaria de petróleo, pois geram efluentes bastante complexos e de difícil tratabilidade. Desta forma, evidencia-se a necessidade de monitoramento contínuo da qualidade desses efluentes, uma vez que são considerados de alto risco. Além do monitoramento físico-químico, o monitoramento biológico é uma importante ferramenta para avaliação da qualidade de efluentes. O objetivo desse trabalho foi avaliar a eficiência de quatro ensaios na determinação da toxicidade de efluente tratado de refinaria de petróleo. Foram realizados ensaios de toxicidade aguda com Daphnia magna e com bactérias aeróbias heterotróficas (Teste D), e ensaios de toxicidade crônica com Ceriodaphnia dubia e Caenorhabditis elegans. Os ensaios com D. magna seguiram a NBR 12713 (ABNT, 2004) e tiveram como endpoint a mortalidade. O Teste D foi baseado em Krebs (1985) e avaliou efeitos de estímulo ou inibição do consumo bioquímico de oxigênio (CBO). Ensaios com C. dubia avaliaram a mortalidade e a reprodução dos organismos, segundo a NBR 13373 (ABNT, 2005). Os ensaios com C. elegans foram realizados de acordo com a ISO/DIS 10872 (2009), e tiveram o crescimento e a reprodução como endpoints. As cinco amostras avaliadas foram provenientes de refinaria de petróleo do estado do Paraná. A análise estatística dos resultados mostrou que C. elegans foi o organismo mais sensível ao efluente, apresentando concentração de efeito observado (CEO) a partir de 12,5%, sendo classificado como organismo moderadamente sensível. Os ensaios com C. elegans e o Teste D apresentaram estímulo na concentração mais baixa, fenômeno conhecido como hormese. Esse fenômeno deveria ser considerado em avaliações ambientais uma vez que toda alteração na composição e estrutura de comunidades interfere na integridade dos ecossistemas. / One of the main sources of water pollution is industrial wastewater. Among these, stands the waste of oil refinery effluents because is quite complex and of difficult tractability. Therefore, it is evident the need for continuous monitoring of the quality of these effluents, since they are considered high risk waste. In addition to monitoring physical and chemical, biological monitoring is an important tool for assessing the quality of effluents. The aim of this study was to evaluate the effectiveness of four tests in determining the toxicity of treated wastewater of oil refinery. Were performed acute toxicity tests with Daphnia magna and heterotrophic aerobic bacteria (D Test), and chronic toxicity tests with Ceriodaphnia dubia and Caenorhabditis elegans. Tests with D. magna followed the NBR 12713 (ABNT, 2004) and had the mortality as endpoint. The D Test was based on Krebs (1985) and assessed the effects of stimulation or inhibition of biochemical oxygen consumption (BOD). Tests with C. dubia evaluated the mortality rate and reproduction of organisms, according to NBR 13373 (ABNT, 2005). Tests with C. elegans were performed according to ISO / DIS 10872 (2009), and had the growth and reproduction as endpoints. The five evaluated samples were from an oil refinery in the state of Parana, Brazil. The statistical analysis showed that C. elegans was the most sensitive organism to the effluent, presenting the observed effect concentration (OEC) from 12.5%, which classified it as moderately sensitive organism. Tests with C. elegans and the D Test showed low-dose stimulation, a phenomenon known as hormesis. This phenomenon should be considered in environmental assessments because every change in communities composition and structure interferes in the ecosystems integrity.

Made available in DSpace on 2017-06-01T18:20:24Z (GMT). No. of bitstreams: 1 Humberto Bezerra de Souza Sobrinho.pdf: 5032111 bytes, checksum: b4117c26a4890c37b51eef2dd5ae6006 (MD5) Previous issue date: 2007-07-26 / Surfactants are amphipathic agents with application in different industries, such as the petroleum, food and pharmaceutic. Many kinds of chemical surfactants are being used nowadays, although the development of alternative products, with biodegradable nature and lower toxicity, as the so called biosurfactants, metabolites from microorganisms, is a sound strategy for the obtention of compounds with ecological acceptability and for the knowledge of specific properties and applications of these compounds. Different biosurfactants have been produced, but few are being commercialized due the production costs regarding the utilization of high cost substrates and the purification techniques. In this work, the possibility of co-utilization of two industrial residues (refinery residue and corn steep liquor) as low-cost substrates for biosurfactant production by Candida sphaerica was investigated. The yeast was cultivated in distilled water supplemented with refinery residue and cornsteep liquor in different concentrations. The results showed a reduction of the medium surface tension to 26 mN/m, with a yield of 4.0 g/L of isolated biosurfactant after 144 hours in medium containing 5.0 % refinery residue and 2.5 % cornsteep liquor. The biosurfactant was characterized as an anionic glycolipid composed of 75 % lipids and 25 % carbohydrates. The metabolic broth free of cells containing the crude biosurfactant was submitted to stability studies related to the surface tension and to the emulsification activity. The biosurfactant showed stable capacity to reduce the surface tension under extreme conditions of pH, temperature and under addition of high sodium chloride concentrations. The biopolymer can also be applied as emulsifier for specific hydrocarbons, considering the importance of the conditions of application. The biosurfactant showed a low micelar critical concentration value (0.08 %) and potential of application in soil bioremediation, which was showed throughout the motor oil removal of 65 %. Regarding the low surface tension associated to the use of industrial residues, the biosurfactant produced by Candida sphaerica shows great potential of application in industrial and environmental processes / Os surfactantes são poderosos agentes anfipáticos de aplicação em indústrias petrolíferas, alimentícias e farmacêuticas, entre outras. Muitos tipos de surfactantes quimicamente sintetizados são hoje utilizados, embora o desenvolvimento de produtos alternativos, biodegradáveis e menos tóxicos, como os chamados biossurfactantes, agentes obtidos por via microbiológica, torna-se uma estratégia importante na obtenção de componentes mais compatíveis com o meio ambiente e na ampliação das propriedades específicas e aplicações desses compostos. Muitos biossurfactantes têm sido produzidos, embora poucos sejam comercializados em virtude do alto custo de produção e dos processos de purificação. Neste trabalho, estudou-se a possibilidade de co-utilização de dois resíduos industriais, milhocina e resíduo de refinaria de óleo vegetal de soja como nutrientes de baixo custo para a produção de biossurfactantes por Candida sphaerica. A levedura foi inicialmente cultivada em água destilada suplementada com milhocina e resíduo de refinaria de óleos vegetais em diferentes concentrações. Os resultados demonstraram redução da tensão superficial do meio para 26 mN/m, com rendimento de 4,5 g/L em biossurfactante isolado após 144 horas de cultivo na presença de 5,0 % do resíduo de refinaria e 2,5 % de milhocina. O biossurfactante foi caracterizado como um glicolipídeo composto por 75 % de lipídeos e 25 % de carboidratos. O líquido metabólico livre de células contendo o biossurfactante produzido foi submetido a estudos de estabilidade frente à tensão superficial e atividade de emulsificação. O biossurfactante apresentou-se estável como agente de superfície sob condições extremas de pH, temperatura e após adição de elevadas concentrações de cloreto de sódio, podendo também ser utilizado como emulsificante de hidrocarbonetos específicos. O biossurfactante demonstrou um baixo valor de concentração micelar crítica (0,08 %) e potencial de aplicação na biorremediação, demonstrado pela remoção de 65 % de óleo de motor adsorvido em areia contaminada. Em função da capacidade de redução da tensão superficial e da utilização de resíduos industriais, o biossurfactante produzido por Candida sphaerica apresenta grande potencial de aplicação em processos industriais e ambientais