Use of anaerobically digested sludge (ADS) in heavy metal removal, was researched. The raw and dewatered ADS samples collected from the effluent of anaerobic digesters and mechanical dewatering units of Ankara City Wastewater Treatment Plant were used. Sorption kinetic and equilibrium tests were conducted using raw ADS at initial pH of 2.0, 4.0 and without adjusting the initial pH. The highest Pb(II) removal capacity was observed as, 8.5 mmol (or 1760 mg) Pb(II) per g of biomass, when the initial pH was not controlled. When dewatered ADS was used Pb(II) removal capacity of ADS was found to drastically decrease to 2.5 mmol (or 518 mg) Pb(II) per g of biomass. Both biomass samples resulted in an increase in the solution pH from an initial value of 4 &ndash / 5 to an equilibrium value of 7 &ndash / 8. Large floc particles settling rapidly were formed after the ADS samples contacted with Pb(II) solution. The high Pb(II) removal capacities, and visual observations during the experiments indicated that precipitation is a dominant mechanism especially at low initial Pb(II) concentrations. FTIR studies showed that carboxyl groups present in the biomass surface of raw ADS were major functional groups in biosorption of Pb(II). The low capacity values attained at initial pH 2.0 indicated that there was a competition between Pb(II) species and hydrogen ions for carboxyl groups. Single and 3-stage fed-batch reactor systems were operated using raw ADS at different initial Pb(II) concentrations. The efficiency of reactor systems increased when 3-stage fed-batch configuration was used and an effluent Pb(II) concentration below 2 mg/L was reached from an initial value of about 200 mg/L.

The removal of toxic and heavy metal contaminants from aqueous waste streams and industrial effluents is one of the most important environmental issues being faced the world over. In order to combat this problem, the commonly used procedures for removing metal ions from dilute aqueous streams include chemical precipitation, ion exchange, reverse osmosis and solvent extraction. However, these techniques have certain disadvantages such as incomplete metal removal, high reagent and energy requirements, generation of toxic sludge or other waste products that require disposal. The hazardous wastes generated from metal mining and smelting operations also need to be decontaminated before entering the ecosystem. Chromium contamination of soil and ground water is a significant problem worldwide. The extensive distribution of this pollutant is due to its numerous industrial applications such as metal plating, alloying, leather tanning and wood industry. Cr (VI) is toxic and carcinogenic in nature while Cr (III) is innocuous. Conventional chromium removal techniques involve reduction to the Cr (III) form and subsequent precipitation as its hydroxide. However, disposal of the solid sludge remains a problem. The search for alternative and innovative treatment techniques has focussed attention on the metal uptake capacities of various microorganisms such as yeast, algae, fungi and bacteria. It is well documented that microbial biomass is capable of adsorbing metal ions from aqueous solution even when the cells have been killed. In the present investigation, the potential of utilising a gram positive, neutrophilic, facultative anaerobe like Bacillus polymyxa, in the bioremoval of Cr (VI) and Cr (III), has been assessed under different conditions. The growth of Bacillus polymyxa has been studied in the presence of varying concentrations of chromium ions. Subsequently, adaptation of the bacteria to Cr (VI) and Cr (III) has also been carried out. The biological reduction of Cr (VI) and its biosorption have been monitored during the growth of the unadapted and 2 ppm Cr (VI) adapted strains. The bioremoval of Cr (VI) and Cr (III) has also been assessed using the metabolic products obtained during bacterial growth. Detailed investigations have been carried out to determine the bioremoval efficiencies of both living and non-living cells of Bacillus polymyxa, with respect to Cr (III) and Cr (VI). The various parameters influencing the bioremoval of chromium by the cells, such as time, pH, wet biomass loading and initial metal concentration, have been studied. Electrokinetic studies on the bacterial cells, before and after interaction with Cr (VI) and Cr(III)have been carried out. The morphological changes induced in the bacterial strains consequent to interaction with Cr (III) and Cr (VI) have been examined by scanning electron microscopy. The results of the present investigation revealed that bioreduction of Cr (VI) was feasible during the growth of both adapted and unadapted bacteria. The time taken for 90% bioremoval was 72 h in the case of the unadapted strain, whereas with the adapted strain only around 48 h were required to achieve comparable results. The metabolic products obtained by enzymatic bacterial action were also found to be efficient in bringing about the bioremoval of Cr (VI). The bioremoval efficiency was marginally better when a lower concentration of Cr (VI) was used. Over 80% bioremoval was achieved in about 10 h using 2 ppm Cr (VI) while almost 48 h were necessary for a similar amount of removal to be effected using 5 ppm Cr (VI). In the case of the metabolite obtained from the adapted strain, complete removal of 2 ppm Cr (VI) was possible in 24 h. The living cells of Bacillus polymyxa were not only able to accumulate Cr (VI) but were also capable of bioreduction to the Cr (III) form, when the pH was in the range of 1.5 to 4. The maximum bioremoval of about 75% of Cr (VI) was observed at pH 2, with 45% being attributed to bioreduction, with an equilibration time of 48 h. In the case of Cr (III) nearly 90% uptake could be achieved at a natural pH of 5.5, equilibration time of 24 h and using 1 g of wet biomass. Biosorption was the only method of removal present in the non-living system. In the case of nonliving biomass, the optimum conditions for maximum Cr (VI) removal (65%) were pH 2, equilibration time of 12 h and a biomass loading of 1 g, whereas for Cr (III), the maximum uptake of about 97% occurred at an initial pH of 5, equilibration time of 12 h and 0.4 g wet biomass. The non-living cells showed a better efficiency in removing Cr (III), while the living cells exhibited a greater tendency towards the bioremoval of Cr (VI) than the non-living ones. Electrokinetic measurements revealed that consequent to interaction with Cr (VI) or Cr (III), significant surface modification was brought about on the cells of Bacillus polymyxa. Further, the isoelectric point was found to be shifted towards less acidic values after interaction with Cr (III) or Cr (VI). The probable mechanisms of the bioremoval processes are highlighted.

<p>Equilibrium isotherms and the adsorption kinetics of heavy metals onto chitosan were studied experimentally. Chitosan, a biopolymer produced from crustacean shells, has applications in various areas, particularly in drinking water and wastewater treatment due to its ability to remove metallic ions from solutions. The adsorption capacity of chitosan depends on a number of parameters: deacetylation degree, molecular weight, particle size and crystallinity. The purpose of this work was to study the adsorption of copper, zinc, mercury, and arsenic on chitosan produced from shrimp shells at a laboratory level.</p><p>The experimental work involved the determination of the adsorption isotherms for each metallic ion in a batch system. The resulting isotherms were fitted using the Langmuir model and the parameters of the equation were determined. Kinetic studies of adsorption for different metallic ions at different concentrations and with different particle sizes were performed in batch and column systems. Simplified models such as pseudo-first-order, pseudo-second-order, and intra-particle diffusion equations were used to determine the rate-controlling step. Some preliminary studies were carried out to address the application of chitosan as an adsorbent in the removal of heavy metals or other metallic ions from natural water and wastewater. The regeneration of chitosan was also studied.</p><p>The results showed that the adsorption capacity depends strongly on pH and on the species of metallic ions in the solution. The optimum pH value for the metallic cation adsorption was between 4 and 6, whereas for arsenic adsorption it was about 3. When the pH is not controlled, the adsorption capacity is independent of the initial pH with the solution reaching a final pH of about 7. It was also found that the Langmuir equation described very well the experimental adsorption data for each metallic ion. The adsorption capacity for the metals on chitosan follows the sequence Hg>Cu>Zn>As.</p><p>The study of the adsorption kinetics of these metallic ions shows that the particle size has a significant influence on the metal uptake rate for copper; but that it has only a slight influence on the adsorption rate of zinc and mercury in the range studied. Arsenic adsorption exhibited an interesting behaviour which depends strongly on the pH of the solution; the uptake increased at short adsorption times and then decreased at long times. The analysis of kinetic models showed that the pseudo-second-order adsorption mechanism is predominant, and the overall rate of the metallic ion adsorption process is therefore controlled by adsorption reactions and not by mass transfer for the range of particle sizes examined in this study.</p><p>With regard to the regeneration of chitosan, it was found that sodium hydroxide is a good agent for zinc and arsenic desorption, whereas ammonium sulphate and sodium chloride were the most suitable for copper and mercury desorption, respectively. The ability of chitosan to remove arsenic from natural water, and copper and zinc from mining waste water was verified. The use of these results for designing purposes is a subject for future work.</p>

Activated sludge microorganisms can remove many hazardous substances from wastewater by adsorbing and concentrating them on their surfaces. Biosorption of these substances onto activated sludge surfaces are influenced by the chemical properties of the substance in question as well as the surface properties of the microorganisms. The purpose of this study is to identify the biosorption mechanisms of heavy metals and the effect of extracellular polymer (ECP) composition of activated sludge on the biosorption of Pb(II), Cd(II), Cu(II), Zn(II) and Ni(II). Microorganisms cultured under different growth conditions are expected to have different compositions of ECPs and hence, different biosorption capacities. For this purpose, three sets of reactors with C/N ratios of 9, representing a carbonlimited case / 21, representing conventional municipal wastewater treatment plant activated sludge and 43, representing nitrogen-limited condition, were set up. The semi continuous reactors were fed synthetically and operated at a sludge age of 8 days. Isotherm and kinetic experiments that were held with three different C/N ratios was indicated that the biosorptive capacity of activated sludge was highly dependent on metal species and the C/N ratio. Although, the dependence of biosorptive capacity on C/N ratio was different for each metal, biosorption properties of activated sludge were found to be directly related with ECP composition. Among the heavy metals tested, Pb(II) was the one that was adsorbed at the highest capacity at all C/N ratios. Also, with the purpose of understanding the mechanism of the process, Ca(II) and Mg(II) ions and carbohydrates released into the solution were also monitored and it was indicated that an ion exchange process is involved in the biosorption of heavy metals especially at high metal concentrations but the whole metal removal can not be explained by ion exchange.

Orientador: Carlos Renato Corso / Banca: Cassiana Maria Reganhan Coneglian / Banca: Sandra Mara Martins Franchetti / Resumo: Entre as questões ambientais mais discutidas pela sociedade, está a poluição pelos diversos ramos da indústria. As indústrias têxteis estão entre os responsáveis pela contaminação, pois, muitas vezes, eliminam seus efluentes sem tratamento adequado nos mananciais, portanto, sem a completa remoção dos corantes. Os corantes azóicos são os mais utilizados pela indústria têxtil e são caracterizados pela presença de grupos azo (N=N). Dos vários métodos de tratamento de efluentes existentes, o tratamento biológico tem sido amplamente estudado. Buscando uma maneira de melhorar o tratamento biológico, o presente trabalho teve como objetivo comparar a capacidade de biossorção e biodegradação do corante azóico Direct Blue 71 em solução pelos fungos Phanerochaete chrysosporium e Aspergillus oryzae, na forma paramorfogênica. Para isso utilizou-se uma solução de corante DB71 a 100 μg/mL. Foram realizados testes de biossorção, por um período de 2 horas, com cinco diferentes concentrações de biomassa e três valores de pH, 2.5, 4.5 e 6.5, sendo que o pH 2.5 proporcionou a melhor condição para a biossorção. A adsorção do corante pela parede celular de ambos os fungos foi avaliado com o auxílio das isotermas de Freundlich, modelo seguido por P. chrysosporium, e Langmuir, seguido por A. oryzae. Para os testes de biodegradação, por 240 horas, utilizou-se apenas uma concentração de biomassa. Com espectrofotometria UV-VIS foi possível determinar porcentagem de descoloração e absorbância relativa do corante após realização dos testes de biossorção e biodegradação, respectivamente. Análises de FTIR permitiram a identificação de moléculas presentes na solução antes e após a biodegradação. Com A. oryzae obteve-se os melhores resultados de biossorção e biodegradação. Contudo, P. chrysosporium também se mostrou eficiente para os tratamentos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Among many environmental issues discussed in society, all sorts of pollution from industrial branches arise as an important matter. Textile industries are responsible by such contamination, since they often eliminate their effluents in the environment without proper treatment, therefore, without complete dye removal. Azo dyes are frequently used in textile industry and characterized by the presence of azo groups (N = N). Of the various methods of wastewater treatment available, biological treatment has been extensively studied. Thus, to improve biological treatment in textile industries, this study aimed to compare the ability of biosorption and biodegradation of Azo dye Direct Blue 71 solution by Phanerochaete chrysosporium and Aspergillus oryzae fungi in paramorfogenic form. In order to achieve this, a 100 μg/mL DB7 dye solution was used. Biosorption tests were performed within two hours with five different biomass concentrations and three pH values, 2.5, 4.5 and 6.5. It was observed that pH 2.5 solutions presented best biosorption conditions. The dye adsorption through studied fungi cell wall was evaluated with the Freundlich isotherm model for P. chrysosporium, and Langmuir for A. oryzae. For the biodegradation tests in 240 hours, it was used only one biomass concentration. Through an UV-VIS spectrophotometry the percentage of relative absorbance and dye discoloration was determined after biosorption and biodegradation tests respectively. FTIR analysis allowed molecular compounds identification in solution before and after biodegradation. The best results were obtained with A. oryzae in both biosorption and biodegradation. Yet even then P. chrysosporium was also efficient in all treatments. Hence, both A. oryzae and P. chrysosporium have great potential of dye removal in wastewaters. These results may contribute to improve effluent treatment systems in textile industries. / Mestre

abstract: To address sustainability issues in wastewater treatment (WWT), Siemens Water Technologies (SWT) has designed a "hybrid" process that couples common activated sludge (AS) and anaerobic digestion (AD) technologies with the novel concepts of AD sludge recycle and biosorption. At least 85% of the hybrid's AD sludge is recycled to the AS process, providing additional sorbent for influent particulate chemical oxygen demand (PCOD) biosorption in contact tanks. Biosorbed PCOD is transported to the AD, where it is converted to methane. The aim of this study is to provide mass balance and microbial community analysis (MCA) of SWT's two hybrid and one conventional pilot plant trains and mathematical modeling of the hybrid process including a novel model of biosorption. A detailed mass balance was performed on each tank and the overall system. The mass balance data supports the hybrid process is more sustainable: It produces 1.5 to 5.5x more methane and 50 to 83% less sludge than the conventional train. The hybrid's superior performance is driven by 4 to 8 times longer solid retention times (SRTs) as compared to conventional trains. However, the conversion of influent COD to methane was low at 15 to 22%, and neither train exhibited significant nitrification or denitrification. Data were inconclusive as to the role of biosorption in the processes. MCA indicated the presence of Archaea and nitrifiers throughout both systems. However, it is inconclusive as to how active Archaea and nitrifiers are under anoxic, aerobic, and anaerobic conditions. Mathematical modeling confirms the hybrid process produces 4 to 20 times more methane and 20 to 83% less sludge than the conventional train under various operating conditions. Neither process removes more than 25% of the influent nitrogen or converts more that 13% to nitrogen gas due to biomass washout in the contact tank and short SRTs in the stabilization tank. In addition, a mathematical relationship was developed to describe PCOD biosorption through adsorption to biomass and floc entrapment. Ultimately, process performance is more heavily influenced by the higher AD SRTs attained when sludge is recycled through the system and less influenced by the inclusion of biosorption kinetics. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2011

Por ser um material de baixo custo e apresentar propriedades ligantes, a macroalga marinha Sargassum filipendula vem sendo utilizada como material biossorvente no processo de biossorção de metais. No presente trabalho a alga marrom foi utilizada no estudo cinético e de equilíbrio dos íons de tório e urânio individuais e os resultados comparados à biossorção desses metais em sistema binário. Os testes foram realizados nas concentrações 1 e 10 mg/L e pH= 1,0 e 4,0 na temperatura de 25 1C. A melhor condição para biossorção de tório foi encontrada para 1 mg/L e pH= 1,0, enquanto que para urânio foi em 1 mg/L e pH= 4,0. O estudo cinético de biossorção de tório mostrou que o modelo de segunda ordem descreve melhor os dados experimentais em 1 mg/L (R2= 0,9987) e 10 mg/L (R2= 0,9919) em pH= 1,0 e 1 mg/L (R2= 0,9976) em pH= 4,0, enquanto em 10 mg/L (R2= 0,9787) pH= 4,0 a curva encontrada representou uma cinética de primeira ordem. Para a cinética de urânio os dois modelos se adequaram bem aos dados em ambas as condições experimentais. O estudo de equilíbrio mostrou um perfil crescente de captação de tório, com uma remoção de 96% e 54% do metal em pH= 1,0 e 4,0, respectivamente, a partir da Co= 1 mg/L. A melhor eficiência de captação dos íons de urânio foi de 33% para Co= 100 mg/L em pH= 1,0 e 71% para Co= 1 mg/L em pH= 4,0. Os dados experimentais da isoterma de tório mostraram-se mais adequados ao modelo de Freundlich para pH= 1,0, enquanto que para o pH= 4,0 esses foram melhor representados pelo modelo de Langmuir, com valores de coeficiente de determinação superiores. Em relação à isoterma do urânio, o modelo de Freundlich representou bem os dados experimentais. Os parâmetros de equilíbrio calculados a partir do modelo de Langmuir (kL, qmax ) e Freundlich (kF, n) indicaram uma maior afinidade da biomassa pelos íons de tório em ambas as condições experimentais. O estudo de equilíbrio do sistema binário mostrou que a biossorção dos íons de tório não é afetada pela presença do urânio em solução. Por outro lado, a sorção do urânio foi fortemente afetada pela coexistência com os íons de tório. / Due to its low cost and ligand properties, the seaweed Sargassum filipendula is highly used as a biosorbent material for metals biosorption processes. In the present work this brown seaweed was used in the kinetic and equilibrium studies of the process of biosorption of thorium and uranium, alone and in combined solutions. Tests were performed in the range of metals concentrations from 1 to 10 mg/L and pH values 1.0 and 4.0 at 25 1C. The best condition for the biosorption of thorium was found in the low concentration of 1 mg/L at pH 1.0, while uranium was best biosorbed at the concentration of 1 mg/L at pH 4.0. The kinetic study of thorium biosorption indicated that the second-order kinetic model best represented the experimental data for the low concentration of 1 mg/L (R2= 0.9987) and 10 mg/L (R2= 0.9919) at pH 1.0; for 1.0 mg/L R2= 0.9976 at pH= 4.0, while for the most concentrated solution (10 mg/L) R2 value was equal to 09787) at pH= 4.0, following a pseudo-first order kinetics. The biosorption of uranium indicated that both kinetic models fitted the experimental data, under both experimental conditions. Equilibrium study showed an increasing thorium biosorption, for increasing initial metal concentration, reaching 96 and 54% recovery of the metal, at pH 1.0 and 4.0, respectively. The higher individual efficiencies observed were 33% biosorption for a 100 mg/L initial concentration at pH 1.0 and 71% for a 1 mg/L concentration, at pH 4.0. Experimental equilibrium data, for the element thorium, indicated a best fit on Freundlich model, at pH 1.0, while at pH 4.0 the results were best represented by the Langmuir model, due to higher determination coefficient values. Considering the uranium isotherm obtained, Freundlich model best represented experimental data, suggesting the formation of a multilayer adsorption on the surface of the biomass. Equilibrium parameters calculated from the Langmuir (kL, qmax) and Freundlich (kF, n) models, indicated a higher affinity of the biomass for thorium, in comparison to uranium in both conditions tested. The study of the binary system equilibrium showed that the biosorption of thorium was not affected by the presence of uranium in solution, due to the same uptake values observed when thorium was solely present in solution, reaching qmax= 85,95 &#956;mol Th/g (individual) and qmax= 110,1 &#956;mol Th/g (mixture). On the other hand, uranium biosorption was markedly affected by the presence of thorium in solution, reaching low or not significant uranium by the biomass. Key words: Biosorption, Sargassum filipendula, Thorium, Uranium.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho teve como objetivo descrever o potencial de biossorção de lantânio pelas microalgas Ankistrodesmus sp. e Golenkinia sp. livres e pellets de alginato de cálcio, com e sem as microalgas imobilizadas, a partir de soluções aquosas. Para isso foram realizados estudos em regime batelada e em coluna de leito fixo. Modelos cinéticos de pseudo-primeira ordem e de segunda ordem e isotermas de equilíbrio de Langmuir e de Freundlich foram utilizados para a descrição quantitativa e a previsão do comportamento de adsorção do metal pelas biomassas livres e imobilizadas no sistema descontínuo. Os dados foram mais bem ajustados pelo modelo cinético de segunda ordem, com coeficientes de determinação (r2) maiores que 0,98. Foram obtidos tempos de equilibrio muito curtos, na faixa de 1-30 minutos. A isoterma de Langmuir foi a que melhor se ajustou aos dados experimentais, com valores de r2 maiores que 0,94. Foram observados valores de qmáx, isto é, a quantidade máxima de metal captado pelo biossorvente, entre 0,96 e 10,43 mmol/g. As células livres mostraram-se mais eficientes do que os pellets caracterizados com e sem os micro-organismos. Os pellets mostraram melhor potencial quando contendo microalgas imobilizadas, em comparação com eles puros. No estudo dinâmico, 12 L de solução contendo uma concentração de La (III) de 150 mmol/L ascenderam pela coluna contendo Ankistrodesmus sp. e Golenkinia sp. imobilizadas e pellets de alginato de cálcio puros durante 8 horas. No último minuto, os três biossorventes ainda apresentaram cerca de 80% de eficiência de remoção. Desta forma, o ponto de satuação não foi atingido. A rápida e alta capacidade de adsorção das microalgas revelou que sua aplicação em escala superior é possível em ambos os processos estudados, uma vez que a imobilização desses biomateriais não mudou a sua capacidade de sorção e nem o rápido contato entre o adsorvente e o soluto no processo de biossorção de lantânio / This study aimed to describe the potential of lanthanum biosorption by microalgal Ankistrodesmus sp. and Golenkinia sp. free and calcium alginate pellets with and without immobilized microalgae from aqueous solutions. To study this system in batch and fixed bed column were performed. Kinetic models of pseudo first-order and second order and equilibrium isotherms of Langmuir and Freundlich were used for the quantitative description and prediction of the behavior of metal adsorption by free and immobilized biomass in a batch system. The data were best fitted by a second-order kinetic model, with coefficients of determination (r2) values greater than 0.98. Very short equilibrium times were obtained in the range of 1-30 minutes. The Langmuir isotherm was the best fit to the experimental data, with r2 values greater than 0.94. qmax, that is, the maximum amount of metal captured by the biosorbent, values between 0.96 and 10.43 mmol/g were observed. The free cells were more efficient than with pellets characterized with and without the microorganisms. The pellets showed good potential when containing immobilized microalgae compared to pure them. In the dynamic study, 12 L of solution containing a concentration of La (III) 150 mmol/L reached by the column containing Ankistrodemsus sp. and Golenkinia sp. immobilized and pure calcium alginate pellets for 8 hours. At the end of the run, the three biosorbents still showed about 80% removal efficiency. Thus, the saturation point was not reached. The rapid and high adsorption capacity of microalgae revealed that its application in a higher scale is possible in both cases studied, since the immobilization of these biomaterials has not changed its sorption capacity or the rapid contact between the adsorbent and the solute in the process biosorption of lanthanum

Os elementos de terras raras, representados em sua maioria pelos lantanídeos, ocorrem principalmente como constituintes-traço da maioria dos minerais de rochas comuns (monazita, apatita) e também estão presentes em alguns minérios. Tais elementos foram largamente usados por décadas como fertilizantes na China. Na área das inovações tecnológicas, a demanda por esses metais vem crescendo por conta das suas aplicações em diversos campos. Consequentemente, grandes quantidades desses elementos são acumulados em ambientes aquáticos atingindo o fitoplâncton. Assim, as microalgas que são organismos ecologicamente importantes na cadeia alimentar têm sido frequentemente usadas em estudos ambientais para avaliar a toxicidade relativa de várias descargas químicas e são largamente estudadas na detecção dos primeiros impactos no ecossistema. Somado a isso, são biomassas que possuem boa capacidade de biossorção de metais devido à presença de ligantes na sua estrutura que promovem a captação deles quando em solução. Dessa forma, as interações entre as microalgas verdes Monoraphidium e Scenedesmus e os íons La3+ e Ce3+ foram investigadas neste trabalho. Para isso, foram avaliados o efeito tóxico e a bioacumulação do La3+ pelas duas microalgas verdes. Adicionalmente, estudos em batelada da biossorção do La3+ e Ce3+ em soluções contendo os elementos isoladamente ou em combinação foram realizados. No estudo de toxicidade e de bioacumulação o meio de cultivo utilizado foi o ASM-1, com e sem presença de La3+ (10 mg.L-1 a 100 mg.L-1), onde o efeito tóxico do metal foi monitorado por análises micro e macroscópica das células e também pela quantificação do crescimento celular baseada em medidas da massa seca. A bioacumulação do metal foi avaliada da mesma forma para ambas as microalgas. Os resultados obtidos mostraram que o efeito tóxico do metal foi presente em concentrações iônicas de 50 e 100 mg.L-1 e que houve uma bioconcentração do La3+ em ambas espécies de microalgas, principalmente quando a concentração inicial do La3+ foi de 10 e 25 mg.L-1, mostrando que houve uma relação direta entre a bioconcentração e a toxicidade do La3+. O gênero Monoraphidium bioconcentrou mais metal que o gênero Scenedesmus. Os resultados da biossorção dos metais em solução monoelementar mostraram que as microalgas apresentaram grande capacidade de captação do La3+ (20,7 mmol.g-1 para Monoraphidium sp. e 17,8 mmol.g-1 para Scenedesmus sp.) e do Ce3+ (25,7 mmol.g-1 para Monoraphidium sp. e 11,5 mmol.g-1 para Scenedesmus sp.). Os resultados obtidos revelaram que os dados melhor se ajustaram ao modelo de Freundlich, na maioria dos casos. Em sistema binário, notou-se que houve uma menor captação de cada um individualmente, evidenciando uma competição entre eles pelos mesmos sítios ligantes e que ambas apresentaram maior afinidade pelo Ce3+ / Rare-earth elements, mostly represented by the lanthanides, usually occur as trace constituents in minerals of some common rocks (monazite, apatite) and also in some ores. Such elements were widely used for decades as fertilizers in China. Regarding technological innovations, the demand for these metals is constantly growing due to their applications in several fields. Consequently, high amounts of these elements are accumulated in the aquatic environment reaching phytoplanctonic species. This way, microalgae, that are the most ecologically relevant species in the food chain, are being frequently used in environmental studies to evaluate relative toxicity from various chemical discharges, also due to their wide use in the detection of the first environmental impacts in ecosystems. Beyond this fact, they constitute a type of biomass with a good metals biosorption capacity due to the presence of ligands in their biological structures, that promote the uptake of metals when present in solution. Thus, the interaction of the Green microalgae Monoraphidium and Scenedesmus with La3+ and Ce3+ were investigated in the present work. To reach this goal, the toxic effect and bioaccumulation of La3+ by both microalgae were studied. Additionally, batch biosorption studies of La3+ and Ce3+ were done, in monoelement and combined solutions were performed. In the study of toxicity and bioaccumulation, the culture medium used was ASM-1 in the presence and absence of La3+ (10 mg.L-1 to 100 mg.L-1), where the toxic effect of the metal was monitored through micro and macroscopic observation of the cultures and also through quantification of the biomass by direct dry mass quantification. In the bioaccumulation tests the same procedure was adopted. The results obtained showed that the toxic effect of the metal was present in 50 and 100 mg.L-1 solutions and that the bioconcentration of La3+ by both species, mainly for La3+ concentrations from 10 to 25 mg.L-1, indicating that there was a direct relation between bioconcentration and La3+ . Cells from the genus Monoraphidium concentrated a higher amount than Scenedesmus. Biosorption results from monoelement solutions showed the high ability of both microalgae to accumulate La3+ (20,7 mmol.g-1 for Monoraphidium sp. and 17,8 mmol.g-1 for Scenedesmus sp.); and, Ce3+ (25,7 mmol.g-1 for Monoraphidium sp. and 11,5 mmol.g-1 for Scenedesmus sp.). The results obtained revealed that experimental data were fitted to Freundlich adsorption model, in most cases. In binary solutions, a smaller uptake was observed, considering individual uptake capacities, thus indicating a competition between the elements for the same ligand sites, and also it was observed a higher affinity for Ce3+

Made available in DSpace on 2014-06-11T19:27:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-04-12Bitstream added on 2014-06-13T19:14:48Z : No. of bitstreams: 1 santos_gc_me_rcla.pdf: 1042770 bytes, checksum: c51bb4a8e2f788a36cdccff91889a12a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Entre as questões ambientais mais discutidas pela sociedade, está a poluição pelos diversos ramos da indústria. As indústrias têxteis estão entre os responsáveis pela contaminação, pois, muitas vezes, eliminam seus efluentes sem tratamento adequado nos mananciais, portanto, sem a completa remoção dos corantes. Os corantes azóicos são os mais utilizados pela indústria têxtil e são caracterizados pela presença de grupos azo (N=N). Dos vários métodos de tratamento de efluentes existentes, o tratamento biológico tem sido amplamente estudado. Buscando uma maneira de melhorar o tratamento biológico, o presente trabalho teve como objetivo comparar a capacidade de biossorção e biodegradação do corante azóico Direct Blue 71 em solução pelos fungos Phanerochaete chrysosporium e Aspergillus oryzae, na forma paramorfogênica. Para isso utilizou-se uma solução de corante DB71 a 100 μg/mL. Foram realizados testes de biossorção, por um período de 2 horas, com cinco diferentes concentrações de biomassa e três valores de pH, 2.5, 4.5 e 6.5, sendo que o pH 2.5 proporcionou a melhor condição para a biossorção. A adsorção do corante pela parede celular de ambos os fungos foi avaliado com o auxílio das isotermas de Freundlich, modelo seguido por P. chrysosporium, e Langmuir, seguido por A. oryzae. Para os testes de biodegradação, por 240 horas, utilizou-se apenas uma concentração de biomassa. Com espectrofotometria UV-VIS foi possível determinar porcentagem de descoloração e absorbância relativa do corante após realização dos testes de biossorção e biodegradação, respectivamente. Análises de FTIR permitiram a identificação de moléculas presentes na solução antes e após a biodegradação. Com A. oryzae obteve-se os melhores resultados de biossorção e biodegradação. Contudo, P. chrysosporium também se mostrou eficiente para os tratamentos... / Among many environmental issues discussed in society, all sorts of pollution from industrial branches arise as an important matter. Textile industries are responsible by such contamination, since they often eliminate their effluents in the environment without proper treatment, therefore, without complete dye removal. Azo dyes are frequently used in textile industry and characterized by the presence of azo groups (N = N). Of the various methods of wastewater treatment available, biological treatment has been extensively studied. Thus, to improve biological treatment in textile industries, this study aimed to compare the ability of biosorption and biodegradation of Azo dye Direct Blue 71 solution by Phanerochaete chrysosporium and Aspergillus oryzae fungi in paramorfogenic form. In order to achieve this, a 100 μg/mL DB7 dye solution was used. Biosorption tests were performed within two hours with five different biomass concentrations and three pH values, 2.5, 4.5 and 6.5. It was observed that pH 2.5 solutions presented best biosorption conditions. The dye adsorption through studied fungi cell wall was evaluated with the Freundlich isotherm model for P. chrysosporium, and Langmuir for A. oryzae. For the biodegradation tests in 240 hours, it was used only one biomass concentration. Through an UV-VIS spectrophotometry the percentage of relative absorbance and dye discoloration was determined after biosorption and biodegradation tests respectively. FTIR analysis allowed molecular compounds identification in solution before and after biodegradation. The best results were obtained with A. oryzae in both biosorption and biodegradation. Yet even then P. chrysosporium was also efficient in all treatments. Hence, both A. oryzae and P. chrysosporium have great potential of dye removal in wastewaters. These results may contribute to improve effluent treatment systems in textile industries.