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Orientador: Carlos Renato Corso / Resumo: A presente pesquisa enfoca a utilização da levedura Candida albicans, isolada de um efluente industrial, em processos de remoção de corantes azóicos. Neste estudo o corante escolhido foi da classe dos diretos, o Direct Violet 51 em solução aquosa. A levedura selvagem foi utilizada na forma de suspensão no estudo da biosorção do corante em diferentes valores de pH comparando o comportamento das células não autoclavadas e autoclavadas, objetivando a remoção do corante em solução aquosa. O corante Direct Violet 51 foi analisado quanto a sua estabilidade espectral em diferentes valores de pH e melhor pH biosortivo, mostrando-se praticamente estável em termos espectrais e o valor de pH 2,5 foi o que melhor se mostrou ativo quanto a capacidade de remover o corante frente as biomassas não autoclavadas e autoclavada de Candida albicans. Em todos os experimentos de interação biosortiva realizados entre a biomassa e o corante, as células autoclavadas foram as que apresentaram uma maior capacidade biosortiva em relação as células não autoclavadas. A avaliação do potencial adsortivo da levedura foi analisado de acordo com as Equações das Isotermas de Adsorção de Freundlich e Langmuir. A comparação entre os coeficientes de correlação das Isotermas de Adsorção indicam que a equação de Langmuir é a que melhor explica a interação da levedura com o corante Direct Violet 51 em todos os valores de pH. O estudo comparativo realizado entre as leituras das amostras pelo aparelho UV-VIS e pelo FT-IR mostraram que há pequenas alterações na estrutura do corante podendo ser um indício de biodegradação. Pelos dados apresentados, o que de fato podemos afirmar é que, do ponto de vista da biosorção, a levedura Candida albicans demonstra habilidade na remoção de substâncias coloridas, tendo potencial enzimático capaz de alterar as estruturas químicas destes pigmentos coloridos que são encontrados em efluentes industriais. / Abstract: The present research focuses the utilization of yeast Candida albicans, isolate of a industrial effluent, in processes of removal of azo-dyes. In this study, the dye used was the Direct Violet 51 that belong the classroom of the direct dyes. The wild yeast was used in the suspension form in the study of the biosorption of the dye in different values of pH, comparing the behavior of the autoclaved cells and not autoclaved cells, objectifying the removal of the dye in aqueous solutions. The dye Direct Violet 51 was analyzed in its spectral stability in different values of pH and was found the better biosorptive pH value, revealing practically steady in spectral terms, and the value of pH 2,50 was what it presented greater capacity to remove the dye front the autoclaved cells and not autoclaved cells of the Candida albicans. In all the experiments of biosorptive interaction carried through between the biomass and the dye, the autoclaved cells had been the ones that had presented a greater biosorptive capacity in relation the not autoclaved cells. The evaluation of the adsorptive potential of the yeast was analyzed in accordance with the equations of the isotherms of adsorption of Freundlich and Langmuir. The comparison between the coefficients of correlation of the Isotherms of Adsorption indicates that the equation of Langmuir is the one that better explains the interaction of the yeast with the dye Direct Violet 51 in all values of pH. The carried through comparative study it between the readings of the samples for the device UV-VIS and for FT-IR, they had shown that it has small alterations in the structure of the dye, being able to be a biodegradation indication. For the obtained data, what we can affirm is that, of the point of view of the biosorption, the yeast Candida albicans demonstrates ability in the colorful substance... (Complete abstract, click electronic address below) / Mestre

Bacteria are known for their abilities to influence the geochemical processes and affect the mobility of contaminants in the subsurface. Arthrobacter strain G975 was studied to improve our understanding of their effect on uranium’s fate and transport. The research experimentally identified and compared several parameters, including cell growth rate, cell viability, and the bacteria partition coefficient, Kd, under various uranium and bicarbonate concentrations mimicking Hanford Site subsurface environmental conditions, as well as the microbes ability to interact with uranyl phosphate minerals. The results show that the G975 strain can uptake up to 90% of the U(VI) concentrations tested, following linear isotherm models whose uptake capacity was measured up to 150.2 ± 71.4 mg/g and decreased with increasing bicarbonate concentrations. AFM and SEM/EDS analysis confirmed surface membrane uranium precipitates. The research presented here is part of a large effort to advance the understanding of the biogeochemistry processes and plausible remediation strategies concerning uranium contamination.

Thesis (Ph.D. (Biochemistry)) --University of Limpopo, 2010 / A heavy-metal resistant bacterium (GM 16) was isolated from a South African antimony mine, and the non-viable cells of the isolate were used to investigate its biosorption capacity for Cd(II) and Cu(II) from aqueous solution in a batch process. The biosorption of both metals were found to be influenced by factors such as pH of the metal solution, initial metal ion and biomass concentrations, rate of agitation, presence of other metal ions, contact time of the metal solution with the biomass and temperature. The initial biosorption of both Cd(II) and Cu(II) was rapid and equilibrium was reached within 1 hour of biomass contact with the metal solutions. The sorption of both metal ions was higher in weak acid than in strong acid conditions and the optimum pH values for Cd(II) and Cu(II) biosorption were 7 and 6, respectively. The presence of the other metal ions in the metal adsorption media influenced the biosorption of both Cd(II) and Cu(II). Mg2+ ions decreased the uptake of Cu(II) and Cd(II) by 4.7 and 6.5 %, respectively. Whereas K+, Na+ and Ca2+ ions increased the uptake of Cd(II) by 12.3, 8.7, and 3.2 %, respectively, they slightly decreased the sorption Cu(II) (2-6.4 %). Increases in initial metal ion (40-120 mg L-1) and biomass (0.8-4.8 g L-1) concentrations enhanced the sorption of Cd(II) and Cu(II) by GM16 biomass. When the biomass concentration was increased from 0.8 to 4.8 g L-1, the biosorption capacity of Cd(II) increased from 5.5 to 14.5 mg g-1 while that of Cu(II) increased from 2.8 to 14.7 mg g-1 at optimum pHs and a temperature of 40 °C. Maximum adsorption of both metals occurred at an agitation rate of 100 rpm. In addition, increase in initial metal ion concentration from 40-120 mg L-1 increased the initial adsorption rates (h) and the equilibrium metal sorption capacity (qe) of the GM 16 biomass from 6.07 to 16.51 mg g-1 for Cu(II) and 8.9 to 17.9 mg g g-1 for Cd(II). Adsorption equilibrium data for both metal ions fitted well to the Langmuir adsorption model with high correlation coefficients (r2 > 0.90) but the data for Cu(II) could also be described by the Freundlich adsorption model. Increase in temperature from 25-40 °C only caused marginal increases in maximum metal sorption capacities (qmax). The results on kinetic analysis showed that the biosorption processes of Cd(II) and Cu(II) ions by the non-viable GM 16 cells followed pseudo-second order kinetic model betterthan the pseudo-first order model, although the calculated metal sorption capacities obtained with the model were overestimated. The calculated thermodynamic parameters showed that the biosorption of Cd(II) and Cu(II) ions was feasible, spontaneous and slightly endothermic for Cd(II) but slightly exothermic for Cu(II) under examined conditions. Based on 16S ribosomal DNA sequencing, the bacterial isolate (GM 16) was identified as a Bacillus sp. and is closely related to Bacillus thuringiensis and Bacillus cereus strains. The biosorption capacity of the non-viable GM 16 biomass was higher than the biosorption capacity reported for the viable GM 16 cells, 65 % of Cd(II) was removed by non-viable biomass whereas 48 % was removed by the viable biomass. For the biosorption of Cu(II), the % metal ion adsorbed for the non-viable GM 16 cells was slightly higher than the % adsorbed for the viable cells although not statistically significant. Only 67 % of Cu(II) was removed by the non-viable cells whereas 65 % was removed by the viable cells. / National Research Foundation

Poly(1-methylpyrrol-2-ylsquaraine) (PMPS) particles are a fine blue-black insoluble powder. Scanning electron microscopy (SEM) pictures reveal that the PMPS particles are microspheres with diameters ranging from 1.3 - 4 micrometers (distribution peaking at 1.9 micrometers). The absorption capacity values of PMPS particles were studied for a large majority of the elements in the periodic table in order to establish a pattern or trend in absorption. The elements specifically targeted at the beginning of the research were the biological elements vital to sustain life and the heavy metals that pose a threat to the environment via pollution and poisoning. Fifty-four elements were investigated in total and all absorbed in varying amounts ranging from 0.01 mmol/g for caesium up to 5.66 mmol/g for phosphorous. It was found that varying the initial elemental compound, temperature and solvent concentrations vastly altered the amount of element absorbed. The majority of elements absorbed best when dissolved in hot concentrated hydrochloric acid at 50oC, some preferred cold conditions (4oC) and/or a neutral solvent (water). The freshness of the elemental compound had a huge impact on the absorption capacities, i.e. new compounds absorbed much better than old stock. A comparison between chloride salts and the hydroxides of Group 1 alkali metals revealed that the hydroxides absorbed much better than the salts, sometimes with more than a ten-fold increase. Release profiles were studied for PMPS particles containing eleven different elements when subjected to an aqueous medium. The study focused on some of the elements that are commonly utilised in industry and also the soft acids and bases primarily because they had some of the highest sorption values and the fact that the majority are known to be particularly toxic to man. The amount of ions released varied enormously ranging from 0% release for selenium up to 83% for arsenic. It was interesting to observe that arsenic had the highest percentage release despite having the lowest sorption uptake and selenium had the lowest (zero) percentage release despite having one of the highest sorption uptakes. Analysis of the release data revealed that there appears to be two types of profile emerging. In the first type of profile the metallic ions leached out of the PMPS particles slowly over a period of time until equilibrium was reached whereupon no more ions were released. This happened for the arsenic, copper, lead, mercury, cadmium, silver and gold ions. In the second type of profile all of the free ions were released as soon as water was added, in the first 2 mL aliquot. This happened for the manganese, sodium and caesium ions. It would appear that the ions that have the gradual release profile are the heavier ions on the right hand side of the periodic table, which also means that they are soft acids or bases. The ions that have the second type of profile, where release was achieved in the first aliquot are situated on the left hand side of the periodic table and were all found to be hard acids. Over-coating studies using PMPS particles containing copper and sodium were separately investigated. The results revealed that PMPS-Cu particles when overcoated with a polymer do appear to have a slow release profile.

Les contaminations des sols par les éléments traces métalliques constituent la deuxième contamination la plus importante au niveau mondial avec plus de 5 millions de sites contaminés répertoriés. Cette contamination est devenue globale et diffuse au sein des écosystèmes et présente des risques non négligeables pour l'environnement, l'économie agricole et la santé publique. Cd, Cu et Pb sont parmi les métaux les plus représentés et/ou les plus à risque de cette contamination. Les comportements difficilement prévisibles des métaux au sein de la matrice sol complexifient les stratégies de remédiation. Les méthodes biologiques représentent une alternative économique, écologique et efficace. Le potentiel des champignons est de plus en plus étudié dans ce domaine.Notre travail propose de mesurer la tolérance et les capacités de biosorption de 28 isolats fongiques issus de sols contaminés et de sélectionner les isolats les plus efficaces pour des essais en microcosmes de sols contaminés. Ainsi, 3 isolats ont été sélectionnés. Absidia cylindrospora tolère 1000 mg.L-1 de Cd en milieu gélosé et biosorbe plus de 50% de Cd et Pb en milieu liquide après 3 jours d'exposition. Coprinellus micaceus biosorbe 100% de Pb en milieu liquide. Enfin, Chaetomium atrobrunneum biosorbe plus de 50% de ces 3 métaux en milieu liquide, après 3 jours d'exposition.Les essais en microcosmes de sols révèlent que les capacités de colonisation de la matrice par l'isolat fongique sont essentielles afin d'avoir une influence significative sur la fraction potentiellement mobile des métaux. Ainsi, A. cylindrospora montre le meilleur potentiel des isolats testés en bioaugmentation. Au bout de 20 jours de traitement, cette espèce est capable de diminuer la fraction potentiellement disponible de Cd de 5% et de Cu de 7%. Des essais complémentaires semblent nécessaires afin d'améliorer le processus (traitement plus long avec un apport de biomasse fongique plus important) et de mieux comprendre les transferts d'ETM au sein du sol en présence de champignons. / Soil contaminations by trace metals are the second most frequent contamination in the world, counting more than 5 million polluted sites. This contamination represents a risk for the environment, the economy, the agriculture and the public health. Cd, Cu, and Pb are among the most frequent and/or toxic elements of this contamination. The hardly predictable behavior of trace metals in the soil matrix turn the remediation methods into a complex issue. Biological methods could be an economic, eco-friendly, and efficient alternative. The potential of the Fungi is more and more studied in this field.Our work aim is to evaluate the tolerance and the biosorption abilities of 28 fungi isolated from polluted soils, and to select the most efficient ones to perform microcosm's experiments of polluted soils. Thus, 3 fungal isolates have been selected. Absidia cylindrospora tolerates 1000 mg.L-1 in agar medium and biosorbs more than 50% of Cd and Pb after 3 days in liquid medium. Coprinellus micaceus biosorbs 100% of Pb in liquid medium. Finally, Chaetomium atrobrunneum biosorbs more than 50% of each metals after 3 days of exposure in liquid medium.The microcosm's experiments reveal that the colonization abilities of the isolates is crucial to enhance the influence of the fungal development on the potentially mobile metal fraction. Thus, A. cylindrospora shows the best potential among the tested isolates in bioaugmented microcosms in order to decrease the potentially mobile fraction of the metals. After 20 days, this isolate decrease the potentially mobile fraction of Cd and Cu respectively by 5 and 7%. Complementary experiments are needed to improve the process (longer experiment, higher fungal biomass) and to better understand the transfers of the metals in presence of fungal organisms.

Nickel contaminated wastewater from plating industries is a major environmental concern. Current treatment methods are often expensive and can also create additional problems. Biosorption is an alternative treatment method that uses inexpensive biomaterials to sequester metals from aqueous solutions. In this study, acid washed barley straw (AWBS) was used for adsorbing nickel ions (Ni2+) from simulated nickel plating wastewater. The adsorption process was rapid and the equilibrium was reached in about an hour. An increase in the initial nickel concentration increased the equilibrium nickel uptake, and the maximum uptake was found to be 8.45 mg/g of AWBS when the initial nickel concentration was1000 mg/L at pH 5. Nickel adsorption was favorable at room temperature than 5oC and 40oC, better adsorption rate and equilibrium uptake was observed at 23oC. Increasing the pH from 3 to 7 increased the equilibrium nickel uptake and the maximum uptake was observed at pH 7, whilst the initial nickel ion concentration was 100 mg/L. The Freundlich isotherm model exhibited better fit with the equilibrium data than the Langmuir equation. Nickel was desorbed using hydrochloric acid solution at pH 2 and the desorption efficiency was 86%. FT-IR studies indicated the participation of hydroxyl, carboxyl and amide groups from cellulose, hemi-cellulose, protein and lignin of barley straw.

Nickel contaminated wastewater from plating industries is a major environmental concern. Current treatment methods are often expensive and can also create additional problems. Biosorption is an alternative treatment method that uses inexpensive biomaterials to sequester metals from aqueous solutions. In this study, acid washed barley straw (AWBS) was used for adsorbing nickel ions (Ni2+) from simulated nickel plating wastewater. The adsorption process was rapid and the equilibrium was reached in about an hour. An increase in the initial nickel concentration increased the equilibrium nickel uptake, and the maximum uptake was found to be 8.45 mg/g of AWBS when the initial nickel concentration was1000 mg/L at pH 5. Nickel adsorption was favorable at room temperature than 5oC and 40oC, better adsorption rate and equilibrium uptake was observed at 23oC. Increasing the pH from 3 to 7 increased the equilibrium nickel uptake and the maximum uptake was observed at pH 7, whilst the initial nickel ion concentration was 100 mg/L. The Freundlich isotherm model exhibited better fit with the equilibrium data than the Langmuir equation. Nickel was desorbed using hydrochloric acid solution at pH 2 and the desorption efficiency was 86%. FT-IR studies indicated the participation of hydroxyl, carboxyl and amide groups from cellulose, hemi-cellulose, protein and lignin of barley straw.

Azolla filiculoides has been evaluated for the adsorption of trace toxic metals from aqueous solution. The adsorption performance of the material was compared with commercial resins and fitted using the Langmuir and Freundlich models. The Freundlich model described the adsorption of copper and cadmium. Whilst the Langmuir isotherm had the better fit of the mercury data. The assumptions of the Freundlich model include multi-layer adsorption and different functional group binding. Conversely the Langmuir model suggests mono-layer adsorption and can infer single group reactivity. The pH effect on the uptake of the metals was investigated and an increase in removal was observed at higher pH with all the metals studied. The material has been thoroughly characterised using physical methods, such as, scanning electron microscopy X-ray photoelectron spectroscopy and electrophoretic mobility measurements. This enabled conclusions to be made regarding the surface functionality of the solid. Chemical characterisation included direct titrations, revealing a gradual dissociation of acidic groups as the pH increased within the experimental range. Kjeldahl nitrogen and amino acid analysis of several biological materials that have been used in metal sorption experiments showed A. filiculoides as having a large proportion of these cell constituents. The kinetics of metal ion uptake by the biosorbent was investigated and compared with commercially available resins. The kinetics are slower than conventional ion exchange resins and carbon adsorbents but entirely adequate for utilisation in a column process. The mechanism hypothesized for metal ion removal by the biosorbent is primarily attributed to ionogenic groups exchanging ions for copper and cadmium removal. Mercury on the other hand is said to be predominantly involved in a reduction-precipitation reaction on the surface of the adsorbent. Regeneration was successfully accomplished for copper and cadmium after minicolumn trials, with greater than 95 % elution of the metals using 0.1M HCI. The mini column trials showed a sharp breakthrough for these metals singularly and a dynamic equilibrium was observed during multi-metal processing. Mercury removal was much slower and more difficult with the same eluant, achieving a maximum of 50% removal. A method for a semi-continuous biosorbent process has been evaluated and proven to be successful in processing metal laden solution.