No presente trabalho foram estudados os metabólitos gerados no processo de biodegradação do corante Remazol brilliant blue R (RBBR) pelo fungo Tinctoporellus sp. em meio líquido. Foi investigada a descoloração do meio de fermentação causada por o processo de degradação, monitorando-se a absorbância da solução durante 17 dias por espectrofotometria UV-Vis. Na presença do fungo Tinctoporellus sp. observou-se uma perda de 90% da coloração do meio de crescimento contendo RBBR 90% em um período de 12 dias. Um experimento de degradação do RBBR em 6 L foi realizado e, após 12 dias, o micélio foi filtrado do meio líquido e os analitos foram extraídos do meio de cultura utilizando-se técnicas de extração em fase sólida. O extrato obtido neste processo foi submetido a separações cromatográficas em gel de Sephadex LH-20, sílica gel derivatizada com grupo C18, assim como purificações por HPLC. Estas separações permitiram o isolamento e identificação de quatro produtos da degradação do corante, derivados antraquinônicos, dos quais três ainda não conhecidos. Além disso, três sesquiterpenos irregulares tremulanos, também inéditos, foram isolados e identificados, a partir do meio de cultura de degradação do RBBR. / In the present study we have investigated metabolites generated during the biodegradation process of the dye Remazol Brilliant Blue R (RBBR), by the action of the marine-derived fungus Tinctoporellus sp. in liquid medium. The decolorization of the fermentation medium caused by the degradation process was monitored by measuring the medium absorbance by UV-Vis during 17 days. The growth medium of Tinctoporellus sp. decolorized up to 90% after 12 days. RBBR degradation experiment with Tinctoporellus sp. performed in large scale during 12 days afforded four dye degradation products, identified as anthraquinone derivatives, three of which not yet new reported in the literature. These anthraquinone derivatives have been isolated by chromatography techniques and identified by spectroscopic analysis. Additionally, three novel tremulane terpenes have also been isolated and identified.

No presente trabalho foram estudados os metabólitos gerados no processo de biodegradação do corante Remazol brilliant blue R (RBBR) pelo fungo Tinctoporellus sp. em meio líquido. Foi investigada a descoloração do meio de fermentação causada por o processo de degradação, monitorando-se a absorbância da solução durante 17 dias por espectrofotometria UV-Vis. Na presença do fungo Tinctoporellus sp. observou-se uma perda de 90% da coloração do meio de crescimento contendo RBBR 90% em um período de 12 dias. Um experimento de degradação do RBBR em 6 L foi realizado e, após 12 dias, o micélio foi filtrado do meio líquido e os analitos foram extraídos do meio de cultura utilizando-se técnicas de extração em fase sólida. O extrato obtido neste processo foi submetido a separações cromatográficas em gel de Sephadex LH-20, sílica gel derivatizada com grupo C18, assim como purificações por HPLC. Estas separações permitiram o isolamento e identificação de quatro produtos da degradação do corante, derivados antraquinônicos, dos quais três ainda não conhecidos. Além disso, três sesquiterpenos irregulares tremulanos, também inéditos, foram isolados e identificados, a partir do meio de cultura de degradação do RBBR. / In the present study we have investigated metabolites generated during the biodegradation process of the dye Remazol Brilliant Blue R (RBBR), by the action of the marine-derived fungus Tinctoporellus sp. in liquid medium. The decolorization of the fermentation medium caused by the degradation process was monitored by measuring the medium absorbance by UV-Vis during 17 days. The growth medium of Tinctoporellus sp. decolorized up to 90% after 12 days. RBBR degradation experiment with Tinctoporellus sp. performed in large scale during 12 days afforded four dye degradation products, identified as anthraquinone derivatives, three of which not yet new reported in the literature. These anthraquinone derivatives have been isolated by chromatography techniques and identified by spectroscopic analysis. Additionally, three novel tremulane terpenes have also been isolated and identified.

Made available in DSpace on 2016-06-02T20:36:38Z (GMT). No. of bitstreams: 1 4321.pdf: 5011742 bytes, checksum: 61d67530b35683f34c3ef4b4e30917aa (MD5) Previous issue date: 2012-03-30 / Financiadora de Estudos e Projetos / Sugarcane bagasse ash is a byproduct of sugar and alcohol industry with potential for field application. However, the presence of organic contaminants such as dioxins turns necessary the development of strategies for removal of those pollutants, such as bioremediation. Because of the high toxicity of dioxins, it is wise to develop effective and low risk methods for initial evaluation of microbial degradation capacity of those compounds by using less dangerous alternatives such as screening tools to select possible microorganisms as candidates for bioremediation. In such context, this work aimed to apply statistical models to evaluate microbial growth capacity under influence of components of a compost windrow already used for other sugarcane industry residues, and also development of qualitative and quantitative methods to evaluate microbial degradation of the dye RBBR and 1,2,3,4-TCDD, molecules selected as model compounds. The Scott-Knott method grouping multiple means showed good results, indicating microbial growth inhibition of all fungi in culture medium with compost windrow, and microbial growth promotion for Aspergillus strains in sugarcane ash doped medium. Furthermore, quantification of RBBR dye in liquid broth was developed, validated and applied through a dilute-and-shoot technique followed by LC-MS/MS, where it was possible to detect up to 4,8pM of dye, being observed a degradation from 40-99% of dye over 30 days. In a similar way, it was developed and validated a GC-MS method to quantify 1,2,3,4-TCDD in liquid broth after extraction, with detection limits of 10ppb, observing a removal of up to 20% of dioxin after 30 days. Another point evaluated was the identification of RBBR degradation products, where it was observed the presence of four dye metabolites during the course of the experiment, which allowed us to propose a degradation pathway of RBBR dye by Aspergillus flavus. / A cinza do bagaço da cana-de-açúcar é um subproduto da indústria sucroalcooleira que apresenta potencial para aplicação no campo. Porém, a presença de contaminantes orgânicos como dioxinas torna necessário o desenvolvimento de estratégias para a remoção destes poluentes, como a biorremediação. Por serem as dioxinas extremamente tóxicas, é sensato o desenvolvimento de métodos eficazes e de baixo risco para avaliação inicial da capacidade microbiana de degradação destes compostos usando alternativas menos perigosas como ferramentas de triagem e seleção de micro-organismos candidatos à biorremediação. Neste contexto, este trabalho teve como objetivo o uso de modelos estatísticos para avaliação do crescimento microbiano em componentes de uma composteira já utilizada para tratamentos de outros resíduos sucroalcooleiros, bem como o desenvolvimento de métodos analíticos qualitativos e quantitativos de avalição da capacidade microbiana de degradação do corante RBBR e da 1,2,3,4-TCDD, moléculas selecionadas como modelos. O agrupamento de médias por Scott-Knott apresentou bons resultados na avaliação do crescimento microbiano, apontando inibição do crescimento de todos os fungos pela composteira, e promoção de crescimento das cepas de Aspergillus no meio com cinza. Ademais, foi desenvolvido e validado um método para quantificação do corante RBBR direto do meio de cultura líquido usando a técnica dilute-and-shoot seguido por LC-MS/MS, onde foi possível detectar até 4,8pM de corante, sendo observada uma degradação entre 40-99% do corante em 30 dias. Da maneira similar, foi desenvolvido e validado um método por GC-MS para quantificação da 1,2,3,4-TCDD em meio líquido após extração, com limites de detecção de 10ppb, onde foi observada uma remoção de até 20% da dioxina em 30 dias de cultivo. Outro ponto avaliado foi a identificação dos produtos de degradação do RBBR durante o experimento, sendo observada a presença de quatro metabólitos do corante nas amostras, o que nos permitiu propor a rota de degradação do corante por Aspergillus flavus.

Treatment of textile wastewaters containing dye materials using the conventional methods based on biological treatment is not possible. In order to overcome this problem, ozonation based on the oxidation of organic pollutants with ozone gas dissolved in aqueous phase have been studied widely. Catalytic ozonation and advanced oxidation processes (AOP) are also used in order to increase the efficiency of sole ozonation In this work, catalytic ozonation processes in the presence of Copper Sulfide (CuS) powder and a synthesized catalyst by the impregnation of iron on alumina (Fe/Al2O3) were studied separately in the treatment of dye solutions, namely Remazol Brilliant Blue-R (RBBR) and Reactive Black-5 (RB-5). Besides catalytic ozonation runs, ozonation parameters and ozonation mechanism were also studied and a model was developed for the semi-batch ozonation. Both catalysts increased the oxidation of side products measured by the decrease in the amount of total organic carbon (TOC) in the treated dye solutions. Dye removal rates were also enhanced in the treatment of RB-5 dye solutions while no significant effect was observed on dye removal rates of RBBR solutions. TOC removals above 90% were observed in the catalytic ozonation using CuS for both of the dye solutions at pH =10 having initial dye concentration of 100 mg/L. The most significant effect of the catalyst addition was observed at pH = 3 where the TOC removals of non-catalytic ozonation were the lowest. CuS addition increased percent TOC removal at the end of the reaction period of 80 min by 123% in the treatment of 100 mg/L RBBR solution, and by 65% in the treatment of 100 mg/L RB-5 solution at pH = 3. On the other hand, addition of Fe/Al2O3 catalyst increased TOC removal of 100 mg/L RB-5 solution by 52 % at pH = 3. In addition, volumetric mass transfer coefficients (kLa) of ozone in the absence and in the presence of a chemical reaction between dye and ozone were estimated from modeling. A correlation for the enhancement factor of ozone absorbed into dye solutions in terms of initial dye concentration was obtained and reported.

Wastewater from the textile industry is difficult to treat effectively due to the prevalent use and wide variety of synthetic dyes that are resistant to conventional treatment methods. White-rot fungi, such as Trametes versicolor, have been found to be effective in decolorizing many of these synthetic dyes and current research is focusing on their application to wastewater treatment. Although numerous studies have been conducted on the ability of both living and nonliving Trametes versicolor to separately decolorize textile dyes, no studies were found to have investigated the use of a mixture of live and dead fungus for decolorization. This study explored potential interactions between live and dead, autoclaved Trametes versicolor biomass in a mixed system by utilizing a series of batch tests with two structurally different synthetic textile dyes. Samples were analyzed by spectrophotometer and compared with controls to determine the effect of any interactions on decolorization. The results of this study indicate that an interaction between living and nonliving biomass occurred that affected the specific dye removal for both Reactive Blue 19, an anthraquinone textile dye, and Reactive Orange 16, an azo textile dye. This interaction was seen to improve the specific dye removal during the first 10-46 hours of experimentation but then diminish the specific dye removal after this period. This effect could be due to hydrophobins, which are surface-active proteins excreted by live fungi that may alter hydrophobicity. Additionally, the presence of adsorptive dead biomass could affect dye contact with degrading enzymes released from the live fungus. By expanding current knowledge of the interactions that take place in a fungal bioreactor and their effect on textile dye decolorization, this research aims to inspire more effective and less costly bioreactor designs for the treatment of textile wastewater.