This thesis evaluates the performance of marine algal-based biosorbents in treating trace metal bearing aqueous solutions. Native seaweed varieties (Ascophyllum nodosum, Lessonia flavicans, Durvillea potatorum and Laminaria hyperborea) were selected on the basis of their varying algin composition as well as their characteristic mannuronic/guluronic acid content. Dealginated seaweed residues, i.e. waste materials arising during algin extraction from brown marine algae were also evaluated as potential metal biosorbent materials. The biosorbents showed significant metal sorption capacity for copper, cadmium, nickel and zinc from synthetic single metal and multi-metal bearing aqueous solutions. The equilibrium biosorption process may be described using a surface complex formation model. Copper biosorption involved chelation-type surface reactions as well as ion exchange whereas nickel and zinc biosorption may be described by simple ion exchange and electrostatic interactions between metal ions and the negatively charged algal surface. Evidence of stoichiometric release of protons upon metal biosorption has been found. Metal biosorption was found to be dependent upon transport limitations due to intraparticle diffusion. Surface functional groups within algal biosorbents that are responsible for metal-ion binding were identified in an attempt to understand the mechanisms of metal biosorption. Physical and chemical characterization techniques such as potentiometric titrations and esterification were used for surface acidity measurements, nitrogen sorption porosimetry for surface area and pore size distribution analysis and FT-IR spectroscopy to identify carboxyl groups attached to structural polysaccharides in algae. Performance of native and dealginate algal fixed-bed mini-columns provided optimum operating conditions for dynamic exchange between metal ions in solution and the algal biomass. Selected biosorbents were successfully employed to treat real industrial metal-plating rinse waters. The most efficient eluants for regeneration of metal-laden biosorbent columns were also identified.

A significant challenge in large scale industrial production of butanol is its low product titer. Butanol needs to be purified to higher than 99% purity in order to be used for fuel applications. The focus of this study is to selectively remove water from butanol-water vapor to achieve fuel grade butanol in a pressure swing adsorption (PSA) system using biosorbents developed from agricultural byproduct canola meal (CM). CM was characterized by Fourier Transform Infrared Spectroscopy (FTIR) that CM contains polar groups such as hydroxyls, carboxyls, and amines in cellulose, hemi-cellulose and protein that have the potential for water adsorption. Physico-chemical characterizations were also done to understand the major composition, elemental make-up, devolatilization characteristics and particle size distribution of the CM used. The results demonstrated that biosorbent based on CM was able to successfully dry lower grade butanol and generate fuel grade butanol of over 99 v/v%. Five operating parameters were studied at two different levels to get the optimum process conditions for butanol drying, including temperature (95 and 111°C); pressure (135 and 201 kPa); feed butanol concentration (55 and 95 v/v %); feed flow rate (1.5 and 3 mL min-1) and particle size of adsorbent (0.425-1.18 mm and 4.7 mm pellets). Orthogonal array design (OAD) tool was used to design experiments and to evaluate the effects of these parameters. The performance of butanol dehydration was evaluated using five indices - water uptake; butanol uptake; water selectivity; butanol recovery; and maximum effluent butanol concentration in the effluent. The results demonstrated that feed butanol concentration, temperature and pressure were found to be the most significant factors overall, affecting most of the indices. The effects of individual operating parameters on each butanol dehydration index were determined and a set of optimum operating conditions were proposed by the range analysis of the orthogonal array design at 111oC, 135 kPa, feed butanol concentration of 55 v/v%, feed butanol-water liquid flowrate of 3 mL/min and biosorbent particle size of 0.43-1.18 mm. The experiments conducted at the above mentioned optimum conditions resulted in water uptake of 0.48 g/g-ads, water selectivity of 5.4, butanol recovery of 90%, and the maximum butanol concentration in the effluent being over 99 v/v% , which are better than that obtained at any other conditions investigated in this work. The Dubinin–Polanyi model based on adsorption potential theory displayed a goodness of fit to the water adsorption isotherm data with a r2 value of 0.95 and average relative error of just 3.5%. The mean free energy determined from the model was 0.02 kJ/mol indicated the adsorption is physical. Thermodynamic parameters were also evaluated which revealed that the water adsorption is exothermic and spontaneous. Water saturated adsorbent was regenerated at 110°C under vacuum and reusability was studied. The contribution of two major components of CM namely cellulose and protein were also examined for their capability to selectively remove water from butanol. The results showed both of them were able to dry water, however cellulose was found to have a higher water uptake and water selectivity than protein, indicating that it plays a major role in drying butanol. In order to compare the performance of CM on drying of butanol with other biomaterials, adsorption experiments were done using corn meal as adsorbent, which is one of the most common starch based biosorbents for ethanol drying. The results demonstrated that canola meal had a higher water uptake and water selectivity than corn meal. Use of CM over corn meal adsorbent is also desirable so as to avoid placing pressure on food consumption. In addition, drying of butanol using other cellulose based biosorbents such as oat hull was also explored. Oat hull demonstrated a potential to adsorb water and dehydrate butanol, which requires further in-depth investigation.

Acidentes ambientais vêm ocorrendo ao longo de décadas, assim, além de atitudes para evitar esses danos, são necessárias ações para remediação. Materiais tecnológicos e de baixo custo em impacto ambiental podem ser uma alternativa para o tratamento de corpos hídricos degradados, além de um caminho ambientalmente sustentável para remediação de córregos e rios urbanos. Neste contexto, buscou-se avaliar na pesquisa, materiais biossorventes para serem utilizados em acidentes de derramamento de derivados do petróleo em meio aquático. Como matéria-prima, utilizaram-se as fibras das cascas de banana, coco e laranja. Como contaminantes foram utilizados a gasolina e o óleo diesel. Os biossorventes foram produzidos por processos de secagem, ativação química, moagem, classificação granulométrica, caracterização e ensaios de sorção. Para a caracterização foram empregadas as técnicas: picnometria, termogravimetria, análise elementar, microscopia eletrônica de varredura, teor de umidade, retenção de água pela biomassa seca, hidrofobicidade, flutuabilidade, teor de cinzas, fluorescência de raios X e classificação granulométrica. Para o tratamento dos dados, desenvolveu-se um planejamento estatístico de identificação das variáveis significativas no processo de sorção, construíram-se curvas de equilíbrio e de cinética de sorção e que foram modeladas por meio das isotermas de Freundlich e Langmuir. Para estudo da influência da granulometria na sorção, os ensaios foram realizados com os grãos primeiramente de maneira generalizada e posteriormente separados por granulometrias distintas. Os resultados se mostraram promissores, sendo o coco o biossorvente mais eficiente, ele sorveu uma média de 3,94 g/g de óleo diesel e 2,80 g/g de gasolina. / Environmental accidents have been occurring for decades, then, in addition to attitudes to avoid such damages, remediation actions are required. Technological materials of low cost and environmental impact may be an alternative for the treatment of degraded water bodies, besides an environmentally sustainable way for remediation of streams and urban rivers. In this context, it was sought to evaluate, in the research, biosorbent materials to be used in accidents of spill of oil derivatives in aquatic environment. The fibers of the banana, coconut and orange crusts were used as raw material. Petrol and diesel were used as contaminants. The biosorbents were produced by processes such as, drying, chemical activation, milling, sorting, characterization and sorption tests. For the characterization, the techniques used were: picnometry, thermogravimetry, elemental analysis, electron microscopy, moisture content, water retention by dry biomass, hydrophobicity, buoyancy, ash content, X - ray fluorescence and granulometric classification. For the treatment of the data, a statistical design was developed to identify the significant variables in the sorption process, equilibrium and sorption kinetics curves were constructed and modeled, using the Freundlich and Langmuir isotherms. To study the influence of granulometry on sorption, the tests were performed with the grains first generalized and later separated by different granulometries. The results were promising, with coconut being the most efficient biosorbent, it had an average of 3,94 g/g of diesel oil and 2,80 g/g of gasoline.

Acidentes ambientais vêm ocorrendo ao longo de décadas, assim, além de atitudes para evitar esses danos, são necessárias ações para remediação. Materiais tecnológicos e de baixo custo em impacto ambiental podem ser uma alternativa para o tratamento de corpos hídricos degradados, além de um caminho ambientalmente sustentável para remediação de córregos e rios urbanos. Neste contexto, buscou-se avaliar na pesquisa, materiais biossorventes para serem utilizados em acidentes de derramamento de derivados do petróleo em meio aquático. Como matéria-prima, utilizaram-se as fibras das cascas de banana, coco e laranja. Como contaminantes foram utilizados a gasolina e o óleo diesel. Os biossorventes foram produzidos por processos de secagem, ativação química, moagem, classificação granulométrica, caracterização e ensaios de sorção. Para a caracterização foram empregadas as técnicas: picnometria, termogravimetria, análise elementar, microscopia eletrônica de varredura, teor de umidade, retenção de água pela biomassa seca, hidrofobicidade, flutuabilidade, teor de cinzas, fluorescência de raios X e classificação granulométrica. Para o tratamento dos dados, desenvolveu-se um planejamento estatístico de identificação das variáveis significativas no processo de sorção, construíram-se curvas de equilíbrio e de cinética de sorção e que foram modeladas por meio das isotermas de Freundlich e Langmuir. Para estudo da influência da granulometria na sorção, os ensaios foram realizados com os grãos primeiramente de maneira generalizada e posteriormente separados por granulometrias distintas. Os resultados se mostraram promissores, sendo o coco o biossorvente mais eficiente, ele sorveu uma média de 3,94 g/g de óleo diesel e 2,80 g/g de gasolina. / Environmental accidents have been occurring for decades, then, in addition to attitudes to avoid such damages, remediation actions are required. Technological materials of low cost and environmental impact may be an alternative for the treatment of degraded water bodies, besides an environmentally sustainable way for remediation of streams and urban rivers. In this context, it was sought to evaluate, in the research, biosorbent materials to be used in accidents of spill of oil derivatives in aquatic environment. The fibers of the banana, coconut and orange crusts were used as raw material. Petrol and diesel were used as contaminants. The biosorbents were produced by processes such as, drying, chemical activation, milling, sorting, characterization and sorption tests. For the characterization, the techniques used were: picnometry, thermogravimetry, elemental analysis, electron microscopy, moisture content, water retention by dry biomass, hydrophobicity, buoyancy, ash content, X - ray fluorescence and granulometric classification. For the treatment of the data, a statistical design was developed to identify the significant variables in the sorption process, equilibrium and sorption kinetics curves were constructed and modeled, using the Freundlich and Langmuir isotherms. To study the influence of granulometry on sorption, the tests were performed with the grains first generalized and later separated by different granulometries. The results were promising, with coconut being the most efficient biosorbent, it had an average of 3,94 g/g of diesel oil and 2,80 g/g of gasoline.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-09-16T14:08:01Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE GARRETT FINAL - 18.05 - IMPRESSÃO.pdf: 2823940 bytes, checksum: 11d5e72c3c2f86d850cb1aeceab5cb36 (MD5) / Made available in DSpace on 2016-09-16T14:08:01Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE GARRETT FINAL - 18.05 - IMPRESSÃO.pdf: 2823940 bytes, checksum: 11d5e72c3c2f86d850cb1aeceab5cb36 (MD5) Previous issue date: 2016-02-15 / CAPES / Os íons metálicos estão presentes em muitos processos industriais e, quando descartados ao meio ambiente, de forma inadequada, exigem atenção especial devido ao seu nível de periculosidade pode ocasionar efeitos prejudiciais aos seres vivos e consequentemente tornando-se um sério problema ambiental. A remoção desses contaminantes em efluentes líquidos tem sido tema de muitas pesquisas, mas o desafio consiste em encontrar um método seguro, eficaz e econômico capaz de tratar esses efluentes antes de serem descartados em qualquer corpo de água fluente. O processo de adsorção vem sendo utilizado como eficaz para a remoção de íons metálicos. Neste trabalho são apresentados estudos para avaliar a capacidade de biossorção de Cu2+ e Pb2+ aplicando cascas de camarão da espécie Litopenaeus vannamei e leveduras (Saccharomyces cerevisiae e Saccharomyces carlsbergensis) como biossorventes. As análises da fase aquosa monocomponentes e bicomponentes foram analisados pelo equipamento de absorção atômica. O ponto de carga zero (pHPCZ) determinado foi igual a 6,0 e o tempo mínimo de contato foi de 1 hora para a realização dos ensaios. Foram realizados testes de precipitação por 24 horas, verificando a concentração no início e no final do experimento, além disso, foi verificado a retenção do papel de filtro, valores entre 0,005% e 0,009%. Técnicas de caracterização como MEV com EDS, DSC/TG, TGA/DTA, DRX e infravermelho, foram importantes para o estudo e a confirmação dos parâmetros experimentais, como: Isotermas de adsorção e dessorção, o tamanho dos microporos fator determinante na acessibilidade das moléculas de adsorbato para a superfície interna de adsorção, verificação dos compostos químicos dos biossorventes e comportamento das reações endotérmicas ou exotérmicas. A técnica de planejamento experimental foi aplicada para otimização do processo de biossorção dos íons metálicos utilizando cada utilizando cada um dos biossorventes em estudo, onde as variáveis de entrada escolhidas foram velocidade de agitação, pH e temperatura. Os ensaios referentes ao estudo cinético e do equilíbrio do processo biossortivo com concentração de 20 mg.L-1 de íons metálicos foram realizados em batelada utilizando as melhores condições encontradas através dos planejamentos experimentais fatoriais. A variável temperatura apresentou efeito de maior significância na biossorção do Cu2+ para as duas espécies de levedura seguida da velocidade de agitação, enquanto para a casca de camarão o pH foi a variável mais significativa. O modelo de pseudo-segunda ordem apresentou melhor ajuste ao estudo cinético e equilíbrio da biossorção em todas as soluções metálicas pelas biomassas. Os estudos do equilíbrio da biossorção com concentração de 20 mg.L-1 dos íons metálicos Cu2+ e Pb2+ através da Saccharomyces carlsbergensis e casca de camarão se ajustaram melhor no modelo Langmuir-Freundlich com capacidade de adsorção máxima de 2,7 mg.g-1 e 3,75 mg.g-1 (Cobre – levedura e casca respectivamente) e 3,83 mg.g-1 e 4,29 mg.g-1 (Chumbo – levedura e casca respectivamente) em 30 minutos. E para os experimentos bicomponentes com capacidade adsortiva de 3,69 mg.g-1 e 3,97 mg.g-1 (Cobre e Chumbo – levedura e casca respectivamente) em 30 minutos. Os comportamentos termodinâmicos da adsorção para os íons metálicos foram avaliados de acordo com valores encontrados pela entalpia, entropia e energia livre de Gibbs. Valores positivos de ΔH, ΔS e valores negativos para ΔG, mostraram que a adsorção dos íons metálicos pelos biossorventes foi endotérmica, espontânea, favorável, e que a desordem do sistema aumentou durante o processo de adsorção. / The metal ions are present in many industrial processes, and when discarded to the environment, inappropriately, require special attention due to their level of dangerousness can cause harmful effects to living beings and consequently becoming a serious environmental problem. Removing these contaminants in wastewater has been the subject of much research, but the challenge is to find a safe, effective and economical method to treat the effluent before being discharged into any body of flowing water. The adsorption process is being used as effective for the removal of metal ions. This paper presents studies to evaluate the biosorption capacity of Cu2 + and Pb2 + applying shrimp shells of the species Litopenaeus vannamei and yeast (Saccharomyces cerevisiae and Saccharomyces carlsbergensis) as biosorbents. Analyses of single-component and two-component aqueous phase were analyzed by atomic absorption equipment. The point of zero charge (pHPCZ) determined was equal to 6.0 and the minimum contact time was 1 hour for the tests. precipitation for 24 hours Tests were conducted by checking the concentrations at the beginning and end of the experiment, moreover, was found to retain the filter paper, values between 0.005% and 0.009%. characterization techniques such as MEV with EDS, DSC / TG, TGA / DTA, XRD and infrared, were important for the study and confirmation of experimental parameters, such as isotherms of adsorption and desorption, the size of the micropores determining factor in accessibility of molecules adsorbate to the inner surface adsorption, verification of the chemical compounds of the biosorbents, and behavior of the endothermic or exothermic reactions. The experimental design optimization technique was applied to the biosorption process using each of the metal ions using each of biosorbents in a study where the input variables were chosen stirring speed, pH and temperature. The tests for the kinetic study and balance the biossortivo process with concentration of 20 mg L-1 of metal ions were conducted in batch mode using the best conditions found through the factorial experimental design. The variable temperature showed higher significant effect on biosorption of Cu2 + to the two yeast species followed by agitation speed, while for shrimp shells pH was the most significant variable. The pseudo-second-order model showed better fit to the kinetic study and balance of biosorption on all metal solutions by biomasses. Studies balance of biosorption with concentration of 20 mg L-1 of the metal ions Cu2 + and Pb2 + by Saccharomyces carlsbergensis and shrimp shell set best in the Langmuir-Freundlich model with maximum adsorption capacity of 2.7 mg.g- 1 and 3.75 mg.g-1 (Copper - yeast and shell respectively) and 3.83 mg g-1 and 4.29 mg.g-1 (Lead - yeast and shell respectively) for 30 minutes. And for the experiments bicomponent adsorptive capacity of 3.69 mg g-1 and 3.97 mg.g-1 (Copper and Lead - yeast and shell respectively) for 30 minutes. The thermodynamic behavior of adsorption for metal ions were evaluated according to values found by the enthalpy, entropy and Gibbs free energy. Positive values of ΔH, ΔS and negative values for ΔG, showed that the adsorption of metal ions by biosorbents was endothermic, spontaneous, favorable, and that the system disorder increased during the adsorption process.

Agricultural wastes; Albizia coriaria, Coffea canephora, Cyperus papyrus, Erythrina abyssinica and Musa spp were evaluated for uptake of aqueous Cd2+ and Pb2+ ions in single- and binary-component solutions. Untreated, base-treated and peroxide-treated biomasses were employed in batch studies. The optimal conditions for Cd2+ and Pb2+ ions biosorption were  pH 3.5 – 5 for contact time 3.0 – 3.5 hours and biosorbent dosage 10 – 12.5 g/L. Base-treated biosorbents showed a 10 – 17 %  sorption enhancement for Cd2+ ions and a 1.6 – 2.3 % uptake reduction for Pb2+ ions. The sorption capacities for Cd2+ and Pb2+ ions for base-treated biosorbents were between 1.738 and 1.760 mg g-1 compared to 1.415 – 1.539 mg g-1 for untreated materials. The maximum biosorption of peroxide treated materials in single component media was between 0.819 and 1.595 mg/g for Pb2+ ions and between 0.044 and 1.343 mg/g for Cd2+ ions while in binary component media it was between 0.472 and 1.303 mg/g for Pb2+ ions and between 0.008 and 0.195 mg/g for Cd2+ ions. The pseudo-second order kinetic model suitably fitted the Cd2+ and Pb2+ ions biosorption data with regression coefficients (R2); 0.892 – 1.000 for peroxide-treated materials and 0.9784 – 0.9999 for base-treated biosorbents which implied that the biosorption was mainly a chemisorption process. The base treated biosorbents had better sorption performance for Cd2+ ions than peroxide treated materials and untreated biomass whereas the order for Pb2+ ions biosorption was untreated &gt; base treated &gt; peroxide treated materials. All materials showed superior selectivity for Pb2+ ions biosorption in comparison to that of Cd2+ ions in single- and binary-component media. A. coriaria performed best of the base treated biosorbents while C. canephora performed best amongst peroxide treated materials for Cd2+ and Pb2+ ions biosorption in single-and binary-component media. In the competitive biosorption, Cd2+ ions showed higher synergistic effects than Pb2+ ions although Pb2+ ions were preferentially sequestered even when the Cd2+:Pb2+ ions ratio was increased through 3:2, 2:1, 3:1 and 5:1. Of the three isotherm models evaluated against the experimental data, the Langmuir model generally fitted the sorption data for both metals. Regression coefficients for the Langmuir model were; 0.983 ≤ R2 ≥ 1.000 for single-component and 0.939 ≤ R2 ≥ 1.000 for binary-component solutions which revealed that the biosorption was potentially monolayer. The biosorption equilibrium coefficient                          values and change in Gibbs’ free energy  values showed that Pb2+ ions biosorption was more thermodynamically favoured than that of Cd2+ ions in single-component and binary-component media. The materials studied displayed potential for use as biosorbents for remediation of aqueous Cd2+ and Pb2+ ions. / <p>QC 20140508</p>

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-06-22T11:26:06Z No. of bitstreams: 1 2016 - B?rbara Magalh?es Neto.pdf: 3282939 bytes, checksum: a4ead0ff5e7307971c24940b1bea36a3 (MD5) / Made available in DSpace on 2017-06-22T11:26:06Z (GMT). No. of bitstreams: 1 2016 - B?rbara Magalh?es Neto.pdf: 3282939 bytes, checksum: a4ead0ff5e7307971c24940b1bea36a3 (MD5) Previous issue date: 2016-07-19 / Among the many existing methods for removing heavy metals off the effluents, the adsorption process stands out for being considered most effective, at lower cost. The phenomenon of adsorption consists in a process of the transfer of one or more constituents of a fluid phase to a surface of a solid phase. The adsorption process depends on physical and chemical characteristics, as: structural properties of the adsorbent (porosity, functional groups), adsorbate (ionic radius and coordination number), interaction between adsorbent and adsorbed. New technologies have emerged with focus returned to the use of biological materials with adsorbing properties for the treatment of effluents, in particular, removal and recovery of heavy metals, showing good performance. The main advantages of using natural adsorbents (biosorbents) in the process of sorption are: low waste generation, easy recovery of metals, the possibility of reuse of the adsorbent and lower operating costs, depending on the adsorbent material used in the process. From the foregoing this research used tablets of composite material, formed of recycled low density polyethylene (LDPErec) as polymer matrix and adsorbent materials (coconut fibber FC, chitosan Qui or clay B) and a comparative study using such tablets as adsorbents, to removal of the chromium (III), in order to determine which tablet has a better adsorption of chromium (III).To this end, there were realized three experimental design, where they were evaluated the influence of the size of coconut fibber particles, the composition of LDPErec/Fc, LDPErec/B, LDPErec/Qui, LDPErec/FC/Qui and LDPErec/B/Qui, the concentration of chromium (III) adsorbate and the exposure time of the tablets in the chromium (III) solution. With the results can conclude that the models used in the experimental design were valid for the evaluation of significant variables of this work, as the best chromium (III) removal conditions. That happened to the composition values of 40/60% to the tablets of LDPErec/FC1, LDPErec/FC3 and LDPErec/B. The particle size range of coconut fibber that proved more favourable was smaller particle size (100-120 mesh) in the composition of 40/60 %. The conductivity has been used to predict a chromium (III) sorption model but it proved not to be good parameter / Entre os muitos m?todos existentes para a remo??o de metais pesados em efluentes, o processo de adsor??o destaca-se por ser considerado um dos mais efetivos, com menor custo. O fen?meno da adsor??o consiste em um processo de transfer?ncia de um ou mais constituintes de uma fase fluida para a superf?cie de uma fase s?lida. O processo de adsor??o depende de caracter?sticas f?sicas e qu?micas, como: propriedades estruturais do adsorvente (porosidade, grupos funcionais), do adsorvato (raio i?nico, n?mero de coordena??o) e intera??es entre o adsorvente e o adsorvato. Novas tecnologias t?m surgido com o foco voltado para a utiliza??o de materiais biol?gicos com propriedades adsorventes para tratamento de efluentes, e particularmente, na remo??o e recupera??o de metais pesados, apresentando bom desempenho. As principais vantagens de utiliza??o de adsorventes naturais (biossorventes) no processo de sor??o s?o: baixa gera??o de res?duos, f?cil recupera??o dos metais, a possibilidade de reutiliza??o do adsorvente e menor custo operacional, dependendo do material adsorvente que ? utilizado no processo. A partir do exposto essa pesquisa utilizou pastilhas de materiais comp?sitos, formadas por polietileno de baixa densidade reciclado (PEBDrec) como matriz polim?rica e materiais adsorventes (fibra de coco-FC, quitosana-Qui ou argila-B) e realizar um estudo comparativo utilizando essas pastilhas como adsorventes, na remo??o de cromo (III), a fim de determinar qual apresenta uma melhor adsor??o de cromo. Com esta finalidade, foram realizados tr?s planejamentos experimentais, onde foram avaliadas a influ?ncia da granulometria das part?culas de fibra de coco, a composi??o das pastilhas de PEBDrec/FC, PEBDrec/B, PEBDrec/Qui, PEBDrec/FC/Qui e PEBDrec/B/Qui, a concentra??o do adsorvato de cromo (III) e o tempo de exposi??o das pastilhas a solu??o de cromo (III). Com os resultados p?de-se concluir que os modelos usados nos planejamentos experimentais foram v?lidos para a avalia??o da signific?ncia dessas vari?veis, como para as melhores condi??es de remo??o do cromo (III), as quais aconteceram nos valores de composi??o de 40/60% das pastilhas de PEBDrec/FC1, PEBDrec/FC3 e PEBDrec/B. A faixa granulom?trica da fibra de coco que se mostrou mais favor?vel foi de menor granulometria (100-120 mesh) na composi??o de 40/60%. Utilizou-se a t?cnica de condutividade para predizer um modelo de sor??o de cromo (III), por?m nas condi??es do estudo, a condutividade n?o demonstrou ser um bom par?metro

Submitted by Erika Demachki (erikademachki@gmail.com) on 2017-01-10T17:07:20Z No. of bitstreams: 2 Dissertação - Glalber Luiz da Rocha Ferreira - 2016.pdf: 1694646 bytes, checksum: 0edfdeae06383f7209358539abe161f7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-01-11T09:54:35Z (GMT) No. of bitstreams: 2 Dissertação - Glalber Luiz da Rocha Ferreira - 2016.pdf: 1694646 bytes, checksum: 0edfdeae06383f7209358539abe161f7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-01-11T09:54:35Z (GMT). No. of bitstreams: 2 Dissertação - Glalber Luiz da Rocha Ferreira - 2016.pdf: 1694646 bytes, checksum: 0edfdeae06383f7209358539abe161f7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-08-29 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The existing techniques for removing heavy metals are expensive and are often not effective. Thus the application arises from biosorbents, an emerging technology that needs to be studied and explored, in order to promote better environmental and human life quality. The study craved verify removal capacity in synthetic aqueous solutions of ions Cr (VI) at concentrations of 10, 25, 50, 75, 100, 125 and 150 mg/L by biosorption by use of active and inactive fungal biomass Pleurotus ostreatus. In the use of the active biosorbent, kinetic studies revealed that in 336 hours was achieved 100% of its saturation capacity at concentrations of 10 and 25 mg/L of Cr (VI), achieving total removal of Cr (VI) in the order of 250 times over the recommended limit for industrial effluents in CONAMA Resolution nº 430/2011, and 360 hours biomass reached its maximum capacity of saturation, reaching values of 98,18% and 96,84%, in concentrations of 50 and 75 mg/L of Cr (VI), respectively. Observing the concentrations of 100% removal was confirmed by analysis of the total EAA chromium values of 141,66 mg/g and 133,55 mg/g biomass respectively. The analysis revealed the micrographs by SEM and TEM we observed at the cellular composition of biomass the presence of bacterial cells associated with the fungus, which on analysis was not possible to know where the metal was in adsorbed, it is better to point out that it was possible to detect content chromium from the cellular structure of the biomass. In the use of the idle biosorbent, kinetic studies showed that 6, 10 and 12 minutes it was reaching 100% of its saturation capacity at concentrations of 10, 25 and 50 mg/L of Cr (VI), respectively, achieving total removal Cr (VI) in the order of 500 times over the recommended limit for industrial effluents in CONAMA Resolution No. 430/2011, and in 22 minutes biomass reached its maximum capacity of saturation, reaching values of 73,21% and 55,13% at concentrations of 75 and 100 mg/L of Cr (VI), respectively. The Langmuir model was the one that best fit the experimental data biosorbent P. ostreatus, when evaluating the separation factor (RL), responding to values between zero and 1. Now, considering the values of the coefficient of determination (R2), the Freundlich model fit better due to present higher values in relation to the Langmuir model. / As técnicas existentes de remoção de metais pesados são caras e muitas vezes não são eficientes. Dessa forma surge a aplicação de biossorventes, uma tecnologia emergente que precisa ser estudada e explorada, com o objetivo de promover melhor qualidade ambiental e da vida humana. O estudo almejou verificar a capacidade de remoção em soluções aquosas sintéticas de íons Cr(VI) nas concentrações de 10, 25, 50, 75, 100, 125 e 150 mg/L, através da biossorção pela utilização da biomassa fúngica ativa e inativa de Pleurotus ostreatus. Na utilização do biossorvente ativo, os estudos cinéticos revelaram que em 336 horas foi alcançado 100% de sua capacidade de saturação nas concentrações de 10 e 25 mg/L de Cr(VI), alcançando uma remoção total de Cr(VI) na ordem de 250 vezes em relação ao limite preconizado para efluentes industriais na Resolução do CONAMA nº 430/2011, e em 360 horas a biomassa atingiu sua capacidade máxima de saturação, atingindo valores de 98,18% e 96,84%, nas concentrações de 50 e 75 mg/L de Cr(VI), respectivamente. Observando as concentrações de 100% de remoção, foi confirmando através da análise de EAA valores de crômio total de 141,66 mg/g e 133,55 mg/g de biomassa, respectivamente. Na análise revelada pelas microfotografias por MEV e MET foi possível verificar junto a composição celular da biomassa a presença de células bacterianas associadas ao fungo, que em análise não foi possível saber onde o metal se encontrava adsorvido, mais vale salientar que foi possível detectar conteúdo de crômio junto a estrutura celular da biomassa. Na utilização do biossorvente inativo, os estudos cinéticos revelaram que em 6, 10 e 12 minutos foi alcançando 100% de sua capacidade de saturação nas concentrações de 10, 25 e 50 mg/L de Cr(VI), respectivamente, alcançando uma remoção total de Cr(VI) na ordem de 500 vezes em relação ao limite preconizado para efluentes industriais na Resolução do CONAMA nº 430/2011, e em 22 minutos a biomassa atingiu sua capacidade máxima de saturação, atingindo valores de 73,21% e 55,13%, nas concentrações de 75 e 100 mg/L de Cr(VI), respectivamente. O modelo de Langmuir foi o que se melhor ajustou aos dados experimentais do biossorvente P. ostreatus, quando avaliando o fator de separação (RL), respondendo a valores entre zero e 1. Agora, considerando os valores do coeficiente de determinação (R2), o modelo de Freundlich se ajustou melhor, devido apresentar valores maiores em relação ao modelo de Langmuir.

Orientadora: Profª. Drª. Luísa Helena dos Santos Oliveira / Coorientadora. Profª. Drª. Lúcia Helena Gomes Coelho / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Ciência e Tecnologia Ambiental, Santo André, 2018. / Os metais potencialmente tóxicos promovem a poluição dos compartimentos ar, solo e água e causam danos cumulativos aos ecossistemas por serem recalcitrantes e persistentes. Tecnologias alternativas como a biossorção e a fitorremediação são eficazes para remoção de metais da água. A fim de comparar estas duas tecnologias em ação, em escala laboratorial, o presente trabalho teve como objetivo avaliar a eficiência da remoção dos metais tóxicos Cd e Pb, na concentração inicial de 4 g L-1, de soluções aquosas por duas espécies de macrófitas aquáticas, o Aguapé (Eichhornia sp.) e a Taboa (Typha sp.). Para o ensaio de biossorção as plantas foram lavadas em água corrente, secas naturalmente por 10 dias, seguidas de secagem em estufa, em seguida foram trituradas e peneiradas para padronização do tamanho da biomassa utilizada nos ensaios. A biomassa seca de cada planta foi mantida em contato com as soluções contaminadas com Cd e Pb em intervalos de tempo distintos, até 24 horas. Na fitorremediação as plantas foram lavadas com água corrente, permaneceram em contato com solução de hipoclorito de sódio e enxaguadas com água deionizada. Foram encaminhadas para a casa de vegetação da Universidade Federal do ABC em São Bernardo do Campo, onde permaneceram em contato com a solução nutritiva durante 21 dias para aclimatação. Após a aclimatação as plantas filhas foram coletadas e acondicionadas em frascos de polietileno com as soluções nutritivas contaminadas. Alíquotas foram retiradas em diferentes intervalos. Ao término da fitorremediação as plantas foram digeridas por via úmida do tipo Nitro-Perclórica para avaliação da concentração de metais acumulados em seus tecidos. Para ambos os tratamentos, os ensaios foram realizados em triplicatas e as amostras foram coletadas, filtradas e analisadas por ICP OES. Análises estatísticas foram realizadas utilizando o ANOVA e o Teste-t, com nível de significância de 5%. A remoção média por biossorção pelo Aguapé foi de 80,9% (Cd) e 51,4% (Pb), enquanto a Taboa removeu em média 58,4% (Cd) e 21,1% (Pb). Baseado nesses resultados, constatou-se, estatisticamente, que a biomassa seca do Aguapé tem maior capacidade de remoção de Cd e Pb quando comparada a da Taboa. Na fitorremediação os valores máximos de remoção porcentual, após 21 dias de ensaio, foram de 88,5% (Cd) e 42,6% (Pb) para o Aguapé e de 82,0% (Cd) e 42,3% (Pb) para a Taboa. Análises estatísticas indicam que não há diferenças significativas na remoção dos metais entre as macrófitas na tecnologia de fitorremediação. A análise dos metais retidos nos tecidos vegetais (q) do Aguapé apresentou os valores máximos de 18,8 mg g-1 (Cd) e de 8,6 mg g-1 (Pb) e a Taboa de 15,0 mg g-1 (Cd) e de 4,6 mg g-1 (Pb) na biossorção. Na fitorremediação a concentração na biomassa do Aguapé foi de 3,2 mg g-1 (Cd) e 4,28 mg g-1 (Pb) e de 5,0 mg g-1 (Cd) e 2,3 mg g-1 (Pb) na Taboa. Aparentemente, as biomassas secas apresentam um melhor desempenho na remoção de Cd e Pb. / Potentially toxic metals cause pollution of air, soil and water compartments and poses cumulative damages to the ecosystems for being recalcitrant and persistent. Alternative technologies such as biosorption and phytoremediation are effective for metal removal from water. In order to compare these two technologies, in a laboratory scale, the present work had as objective to evaluate the efficiency of the removal of the toxic metals Cd and Pb, at 4 mg L-1 initial concentration, of aqueous solutions by two species of aquatic macrophytes, Water hyacinth (Eichhornia sp.) and Cattail (Typha sp.). For biosorption assay the plants were washed in tap water, dried naturally for 10 days, followed by oven drying, then crushed and sieved to standardize the size of the biomass used in the tests. The dry biomass of each plant was kept in contact with the solutions contaminated with Cd and Pb at different time intervals, up to 24 hours. In phytoremediation the plants were washed with tap water, remained in contact with sodium hypochlorite solution and rinsed with deionized water. They were sent to the greenhouse of the Federal University of ABC in São Bernardo do Campo, where they remained in contact with the nutrient solution for 21 days for acclimatization. After acclimatization, the daughter plants were collected and conditioned in polyethylene bottles with contaminated nutrient solutions. Aliquots were withdrawn at different intervals. At the end of the phytoremediation the plants were wet-digested by Nitro-Perchloric type to evaluate the concentration of accumulated metals in their tissues. For both treatments, the tests were performed in triplicates ante the samples were collected, filtered and analyzed by ICP OES. Statistical analyzes were performed using ANOVA and the t-Test, with a significance level of 5%. For biosorption, the mean removal by Water hyacinth was 80.9% (Cd) and 51,4% (Pb), while Cattail removed on average 58,4% (Cd) and 21.1% (Pb). Based on these results, it was statistically verified that the dry biomass of Water hyacinth has greater capacity of Cd and Pb removal when compared to Cattail. In phytoremediation the maximum percentage removal values, after 21 days of testing, were 88.5% (Cd) and 42.6% (Pb) for Water hyacinth and 82.0% (Cd) and 42.3% (Pb) for Cattail. Statistical analyses indicate that there are no significant differences in metals removal among macrophytes in phytoremediation technology. The analysis of the metals retained in plants tissues (q) of Water hyacinth showed the maximum values of 18.8 mg g-1 (Cd) and 8.6 mg g-1 (Pb) and Cattail 15.0 mg g-1 (Cd) and 4.6 mg g-1 (Pb) in the biosorption. In the phytoremediation, the concentration in the biomass of Water hyacinth was 3.2 mg g-1 (Cd) and 4.28 mg g-1 (Pb) and 5.0 mg g-1 (Cd) and 2.3 mg g-1 (Pb) in Cattail. Apparently, dry biomass exhibits better performance in Cd and Pb removal.

Vatten är en förutsättning för allt liv, men det är inte bara vatten som krävs, utan även att vattnet är rent och går att dricka. Det finns goda tillgångar till vatten på vår jord, men bara en bråkdel av detta vatten är av tillräckligt god kvalité för att det ska kunna drickas. Idag saknar fler än 700 miljoner människor i världen tillgång till tjänligt dricksvatten. Uganda är ett av många länder som berörs av detta och många dricksvattenkällor i Ugandas urbana miljöer riskerar dessutom att förorenas av metaller, såsom bly och mangan. Landet är i en kraftig utvecklingsfas, men de ekonomiska resurserna är begränsade. Det är därför viktigt att försöka lösa dricksvattenförsörjningen både snabbt och på ett ekonomiskt fördelaktigt sett. Till följd av att Uganda är ett land rikt på naturresurser så har det börjat undersökas kring möjligheterna att använda biomassa från resterna av vissa jordbruksprodukter för att rena vattnet. I denna studie fokuseras det på två av de största jordbruksprodukterna i Uganda, Coffea canephora och Musa spp, vilka är en sorts kaffeplanta respektive bananplantor. Biomassa från dessa produkter har i tidigare studier visat sig vara teoretiskt lämpade för att rena vatten från metaller. Syftet med denna studie är att fastställa sorptionsförmågan av bly hos biomassa från Coffea canephora och Musa spp för att bidra med ny data och information för praktiskt tillämpning av dessa biomassor vid rening av dricksvatten i Uganda. Detta har genomförts med laboration. I laborationen konstruerades sex olika vattenprover innehållande olika sammansättningar av metallerna bly, mangan och kalcium. Halterna av mangan och kalcium varierades för att fastställa hur deras förekomst påverkade biomassornas sorptionsförmåga av bly. Resultaten visade att både Coffea canephora och Musa spp kan rena vatten, med en ursprunglig blykoncentration av 50 μg/L, så pass bra att blyhalten hamnar under WHOs gränsvärde på 10 μg/L efter sorptionsprocessen. Detta gällde för samtliga vattenprover, trots olika metallinnehåll. Sorptionskapaciteten var för Musa spp från 6,64 μg/g till 7,17 μg/g och för Coffea canephora var den från 5,94 μg/g till 6,40 μg/g. Biomassa från Musa spp hade bättre sorptionsförmågan i jämförelsen mellan de båda biomassorna, oberoende av vattenprovernas olika sammansättningar. Sorptionskapaciteten visade sig dock minska för Musa spp då det fanns mangan men inget kalcium i vattnet. Soprtionskapaciteten för Coffea canephora försämrades då vattenproverna innehöll andra metaller än bly. Utöver detta fanns inget tydligt samband över hur koncentrationen av mangan och kalcium förhöll sig till sorptionsförmågan av bly. Studien har varit begränsad vad gäller tid och resurser. Ytterligare studier behövs för att få en bättre helhetsuppfattning av hur användning av biomassor kan bidra till dricksvatten av god kvalité. Trots detta visade resultaten på bra sorptionsförmåga hos de båda biomassorna, vilket är ett bra underlag för att fortsätta arbeta mot en verklig implementering av biomassornas användning vid dricksvattenrening i Uganda. / Water is the source of all life, but water itself is not the only requirement, the water also needs to be clean and potable. There are good assets to water on our Earth, but only a fraction of this water is of a quality good enough for it to be potable. As of today, more than 700 million people worldwide lack access to drinking water of good quality. Uganda is one out of many countries that are affected by this and many sources of drinking water in Uganda's urban environments also risk to be contaminated by metals such as lead and manganese. The country is undergoing a significant development, but the financial resources are limited. It is therefore important to try to solve the drinking water supply both quickly and economically advantageous. Uganda is a country that is rich in natural resources, and as a result of that, the feasibility of using biomass from the remains of some agricultural products for water purification water has begun to being examined. This study focuses on two of the biggest agricultural products in Uganda, Coffea canephora and Musa spp, which are sorts of coffee plant and banana plants. Biomasses from these products have previously been shown to be theoretically suitable for purifying water from metals. The purpose of this study is to determine the sorption capacity of lead for the biomasses of Coffea canephora and Musa spp. This new data and information can then help with the development of practical application of these biosorbents in drinking water treatment in Uganda. This has been carried out by laboration. In the lab, six different water samples were constructed, all with different compositions of the metals lead, manganese and calcium. The levels of manganese and calcium were varied to determine how their presence affected the sorption capacity of lead for both biomasses. The results showed that both Coffea canephora and Musa spp can purify water, with an initial lead concentration of 50 μg/L, so good that the lead concentration falls below the WHO’s threshold of 10 μg/L after the sorption process. This was true for all water samples, despite of difference in metal content. The Sorption capacity showed to be for Musa spp from 6.64 μg/g to 7.17 μg/g and for Coffea canephora from 5.94 μg/g to 6.40 μg/g. Biomass from Musa spp had better sorption capacity in comparison between the two biomasses, regardless of the different compositions of the water. However, the sorption capacity for Musa spp was reduced when there was manganese but no calcium in the water. The sorption capacity for Coffea canephora deteriorated when there were more metals than lead in the water. Apart from this, there was no clear correlation of how the concentration of manganese and calcium were related to the sorption capacity of lead. This study has been limited in terms of time and resources, therefore further studies will be needed to get a better overall understanding of how the use of biosorbents can contribute to drinking water of good quality. In spite of this, the results prove that both biomasses have a good sorption capacity of lead, which is a good basis for further studies towards a real implementation of biomass use in purification of drinking water in Uganda.