O rejeito radioativo como qualquer outro tipo de resíduo, precisa receber tratamento adequado. É necessário considerar suas características físico-químicas e radiológicas para a escolha da ação apropriada para o tratamento e a deposição final do rejeito. Muitas técnicas de tratamento utilizadas hoje são economicamente dispendiosas, inviabilizando muitas vezes o seu uso e impulsionando o estudo de outras técnicas de tratamento. Uma dessas técnicas é a biossorção, que demonstra alto potencial quando aplicada a rejeitos radioativos. Essa técnica utiliza materiais de origem biológica para a remoção de metais. Dos potenciais biossorventes encontrados, as macrófitas aquáticas apresentam-se vantajosas e possibilitam a remoção do urânio presente no rejeito radioativo líquido a baixo custo. O objetivo deste estudo foi avaliar a capacidade de biossorção das macrófitas aquáticas Pistia stratiotes, Limnobium laevigatum, Lemna sp e Azolla sp no tratamento dos rejeitos radioativos líquidos. Este trabalho foi dividido em duas etapas, uma de caracterização e preparação e outra de ensaios de biossorção, realizados com soluções de urânio e com rejeito real. As biomassas foram testadas na sua forma bruta e os ensaios de biossorção foram realizados em frascos de polipropileno contendo 10 mL de solução de urânio ou 10 mL de rejeito radioativo e 0,20 g de biomassa. O comportamento das biomassas foi avaliado por meio da cinética de sorção e modelos de isotermas. As maiores capacidades de sorção foram observadas com as macrófitas Lemna sp com 162,1 mg/g e para a Azolla sp com 161,8 mg/g. Os tempos de equilíbrio obtidos foram de 1 hora para a Lemna sp, e de 30 minutos para a Azolla sp. Com o rejeito real, a macrófita Azolla sp apresentou uma capacidade de sorção de 2,6 mg/g. Estes resultados sugerem que a Azolla sp possui maior capacidade de biossorção, sendo a mais indicada para estudos mais detalhados de tratamento de rejeitos radioativos líquidos. / Radioactive waste as any other type of waste should be treated and disposed adequately. It is necessary to consider its physical, chemical and radiological characteristics for choosing the appropriate action for the treatment and final disposal. Many treatment techniques currently used are economically costly, often invalidating its use and favoring the study of other treatment techniques. One of these techniques is biosorption, which demonstrates high potential when applied to radioactive waste. This technology uses materials of biological origin for removing metals. Among potencial biosorbents found, macrophytes acquatics are useful because they may remove uranium present in the liquid radioactive waste at low cost. This study aims to evaluate the biosorption capacity of macrophyte acquatics Pistia stratiotes, Limnobium laevigatum, Lemna sp and Azolla sp in the treatment of liquid radioactive waste. This study was divided into two stages, the first one is characterization and preparation of biosorption and the other is tests, carried out with uranium solutions and real samples. The biomass was tested in its raw form and biosorption assays were performed in polypropylene vials containing 10 ml of solution of uranium or 10ml of radioactive waste and 0.20g of biomass. The behavior of biomass was evaluated by sorption kinetics and isotherm models. The highest sorption capacities found was 162.1 mg / g for the macrophyte Lemna sp and 161.8 mg / g for the Azolla sp. The equilibrium times obtained were 1 hour for Lemna sp, and 30 minutes for Azolla sp. With the real waste, the macrophyte Azolla sp presented a sorption capacity of 2.6 mg / g. These results suggest that Azolla sp has a larger capacity of biosorption, therefore it is more suitable for more detailed studies of treatment of liquid radioactive waste.

Rejeitos radioativos líquidos contendo compostos orgânicos precisam de atenção especial, porque os processos de tratamento disponíveis são caros e difíceis de serem gerenciados. A biossorção é uma potencial técnica de tratamento que tem sido estudada em rejeitos simulados. O termo biossorção é utilizado para descrever a remoção de metais, metalóides e/ou radionuclídeos por um material de origem biológica independentemente de sua atividade metabólica. Dentre as potenciais biomassas, os resíduos agrícolas apresentam características muito atraentes, pois possibilitam a remoção dos radionuclídeos presentes no rejeito utilizando um biossorvente de baixo custo. O objetivo deste estudo foi avaliar o uso potencial de diferentes biomassas originadas de produtos ou resíduos agrícolas (fibra de coco, casca de café e casca de arroz) no tratamento de rejeitos radioativos líquidos orgânicos reais. Foram realizados experimentos com essas biomassas incluindo i) Preparação, ativação e caracterização das biomassas; ii) Realização dos ensaios de biossorção e iii) Avaliação do produto da imobilização de biomassas em cimento. As biomassas foram testadas nas formas brutas e ativadas. A ativação foi realizada com soluções diluídas de HNO3 e NaOH. Os ensaios de biossorção foram realizados em frascos de polietileno, nos quais foram adicionados 10 mL do rejeito radioativo ou diluições do rejeito em água deionizada com o mesmo pH e 2 % da biomassa (m/v). No final do experimento, a biomassa foi separada por filtração e a concentração dos radioisótopos remanescente no filtrado foi determinada por ICP-OES e espectrometria gama. O rejeito estudado contém urânio natural (U (total)), amerício-241 e césio-137. Os tempos de contato adotados foram 30 min, 1, 2 e 4 horas e as concentrações estudadas variaram entre 10% e 100%. Os resultados foram avaliados por meio da capacidade máxima de sorção experimental e modelos ternários de isotermas e cinética. As maiores capacidades de sorção foram observadas com casca de café bruta, com valores aproximados de 2 mg/g de U (total), 40 x10-6 mg/g de Am-241 e 50 x10-9 mg/g de Cs-137 e, também, com fibra de coco ativada, com valores de 2 mg/g de U (total), 70 x10-6 mg/g de Am-241 e 40 x10-9 mg/g de Cs-137. As propriedades avaliadas na determinação da qualidade do produto de imobilização foram água livre, resistência mecânica, trabalhabilidade e tempo de pega. Os melhores produtos de imobilização para estas biomassas foram obtidos com uma relação água/cimento de 0,30, contendo 5%, 10% e 15% de casca café bruto, fibra de coco ativada e casca de café ativado, respectivamente. Estes resultados sugerem que a biossorção com casca de café bruta e fibra de coco sob a forma ativada podem ser aplicadas no tratamento de rejeitos radioativos líquidos orgânicos contendo urânio, amerício-241 e césio-137. / Radioactive liquid waste containing organic compounds need special attention, because the treatment processes available are expensive and difficult to manage. The biosorption is a potential treatment technique that has been studied in simulated wastes. The biosorption term is used to describe the removal of metals, non-metals and/or radionuclides by a material from a biological source, regardless of its metabolic activity. Among the potential biomass, agricultural residues have very attractive features, as they allow for the removal of radionuclides present in the waste using a low cost biosorbent. The aim of this study was to evaluate the potential use of different biomass originating from agricultural products (coconut fiber, coffee husk and rice husk) in the treatment of real radioactive liquid organic waste. Experiments with these biomasses were made including i) Preparation, activation and characterization of biomasses; ii) Conducting biosorption assays; and iii) Evaluation of the product of immobilization of biomasses in cement. The biomasses were tested in raw and activated forms. The activation was carried out with diluted HNO3 and NaOH solutions. Biosorption assays were performed in polyethylene bottles, in which were added 10 mL of radioactive waste or waste dilutions in deionized water with the same pH and 2% of the biomass (w/v). At the end of the experiment, the biomass was separated by filtration and the remaining concentration of radioisotopes in the filtrate was determined by ICP-OES and gamma spectrometry. The studied waste contains natural uranium, americium-241 and cesium-137. The adopted contact times were 30 min, 1, 2 and 4 hours and the concentrations tested ranged between 10% and 100%. The results were evaluated by maximum experimental sorption capacity and isotherm and kinetics ternary models. The highest sorption capacity was observed with raw coffee husk, with approximate values of 2 mg/g of U (total), 40 x10-6 mg/g of Am-241 and 50 x10-9 mg/g of Cs-137 and, also, with activated coconut fiber, with values of 2 mg/g of U (total), 70 x10-6 mg/g of Am-241 and 40 x10-9 mg/g of Cs-137. The properties evaluated to determine the quality of the immobilization product were free water, mechanical strength, workability and setting time. The best immobilization products for these biomasses were obtained with a water/cement ratio of 0.30, containing 5%, 10% and 15% of raw coffee husk, activated coconut fiber and activated raw coffee husk, respectively. These results suggest that biosorption with raw coffee husk and activated coconut fiber can be applied in the treatment of radioactive liquid organic wastes containing uranium, americium-241 and cesium-137.

Muitos biossorventes naturais têm sido pesquisados por possuírem baixo custo e apresentarem propriedades ligantes, como é o caso da macroalga marinha Sargassum filipendula (S. filipendula) que vem sendo utilizada como material biossorvente no processo de biossorção de metais pesados. No presente trabalho a alga marrom foi utilizada para estudos realizados em batelada, onde se determinou o pH ideal de biossorção de vanádio, a relação sólido/líquido ideal e a importância da velocidade de agitação. O estudo cinético e de equilíbrio dos íons metálicos também foram realizados em bateladas nas seguintes condições de ensaio: (1) 0,10 g de biomassa, 25,0 mL de solução de vanádio igual a 18,0 mg L-1, temperatura 25,0 C e 150 rpm de agitação; (2) 0,10 g de biomassa, 25,0 mL de solução de vanádio igual a 36,0 mg L-1, temperatura 25,0 C e 150 rpm de agitação. A melhor condição para biossorção de vanádio foi encontrada para 36,0 mg L-1 e pH= 2,0. O estudo cinético de biossorção de vanádio mostrou que o modelo de segunda ordem descreve melhor os dados experimentais em 36,0 mg L-1 (R2= 0,9825). O estudo de equilíbrio mostrou um perfil crescente de remoção de vanádio. A melhor eficiência de captação dos íons de vanádio foi de 61,0 % para Co= 40,0 mg L-1 em pH= 2,0. Os dados experimentais da isoterma de vanádio mostraram-se mais adequados ao modelo de Langmuir para pH= 2,0, Os parâmetros de equilíbrio calculados a partir do modelo de Langmuir (b, qmax ) 0,009 e 43,3 mg/g, respectivamente, corroboram melhor para a interpretação dos resultados quando comparados com o modelo de Freundlich (kF, n) 1,56 e 2,41, visto que o coeficiente de correlação é maior para Langmuir / Many natural biosorbents have been investigated for having low cost and submit binding properties, as is the case of marine marcoalgae Sargassum filipendula (S. filipendula) that has been used biosorbent material in the processes of biosorption of heavy metals. In the present study the brown seaweed has been used to study conducted in bach mode, where it was determined the optimum pH for biosorption of vanadium, the solid/liquid ratio ideal and the importance of speed of agitation. The kinetic and equilibrium study of metal ions were also performed in batches in the following test conditions: (1) 0.10 g of biomass, 25.0 mL of vanadium solution equal to 18.0 mg L-1, temperature 303 K and 150 rpm agitation. (2) 0.10 g of biomass, 25.0 mL of vanadium solution equal to 36.0 mg L-1, temperature 303 K and 150 rpm agitation. The optimum conditions for biosorption of vanadium was found to 36.0 mg L-1, pH 2,0. The kinetic study of vanadium biosorption showed that the second order model best describes the experimental data 36.0 mg L-1, (R2 = 0.9825). The balance study showed an increased uptake profile of vanadium. The best collection efficiency of vanadium ion was 46.0 % for Co = 36.0 mg L-1 at pH 2.0. The experimental isotherm data of vanadium were more suitable for the Langmuir model at pH 2.0. The equilibrium parameters calculated from the Langmuir model (b, qmax ) were 0.009 e 43.3 mg/g respectively, to better corroboration to interpretation of results when compared with the Freundlich model (kF, n) 1,56 e 2,41, whereas the correlation coefficient is higher for Langmuir

Made available in DSpace on 2014-06-11T19:31:00Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-03-25Bitstream added on 2014-06-13T21:01:53Z : No. of bitstreams: 1 oliveira_rc_dr_araiq.pdf: 2354887 bytes, checksum: 89c5b192793995d9542d4827f06031b1 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O processo de biossorção tem sido reconhecido como alternativa potencial na concentração de metais pesados e radioisótopos a partir de corpos d’água que recebem ação antropogênica (indústria, mineração, etc.). A biossorção é um processo que se baseia na remoção de íons metálicos em solução aquosa através de interações entre o metal e determinados sítios ativos presentes em revestimentos celulares, provenientes de biomassas como algas, bactérias e fungos. Na última década, há na literatura um crescente interesse na aplicação deste processo para concentração, recuperação e separação de metais de alto valor agregado e/ou de grande demanda tecnológica, tais como as terras-raras (TR) – essenciais para fabricação de um sem-número de produtos, a citar: laseres, supercondutores, equipamentos miniaturizados, etc. Apesar de apresentarem uma considerável disponibilidade na natureza, as TR possuem alto valor agregado devido aos dispendiosos e complexos processos de separação e purificação de misturas de TR, resultado da alta similaridade química entre os elementos do grupo. Poucos países detêm processos industriais completos de separação destes metais, dessa forma, o domínio dessa tecnologia determina uma importância considerável nos aspectos geopolíticos, estratégicos e econômicos, visto a extensão de investimentos em P&D envolvidos e as descobertas geológicas nas últimas décadas das jazidas chinesas, que abrangem 80% das reservas mundiais. Este trabalho consiste em uma avaliação preliminar da utilização do processo de biossorção na biomassa Sargassum sp. para a concentração, recuperação e separação de misturas de metais TR a partir de soluções sintéticas. As interações metal-biomassa seguem uma cinética de pseudo-segunda ordem e são descritas pelo modelo de adsorção de Langmuir... / The biosorption process has been recognized as potential alternative to concentrate heavy metal and radioisotopes from wastewaters of the anthropogenic activities (industry, mining, etc.). The biosorption is a process based on removal of metallic ions in aqueous solution from interactions among the metal and determined active sites on cellular envelope of biomasses as such algae, bacteria, and fungus. In last decade, there are in the literature a crescent interest to apply this process for the concentration, recovery, and separation of metals of high aggregated value and/or high technologic demand as the rare earth metal (RE), which are essential for the manufacturing of a great number of products; e.g. lasers, superconductors, miniaturized equipments, etc. Despite of the RE present a relevant availability, they have high aggregated value due to expansive and complicate processes of separation and purification of RE mixtures, which is resulted of the high chemical similarities of the group. Few countries have complete industrial processes of separation of these metals, so the domain of this technology determines a considerable importance in geopolitical, economic, and strategic aspects because the extension of R&D investments involved and the geological discoveries of the Chinese ore deposits in the last decades, which comprise 80 % of world reserves. This work consists on evaluation of the biosorption process by Sargassum sp. biomass for the concentration, recovery, and separation of RE metals from synthetic solutions. The metalbiomass interactions follow the pseudo-second-order kinetics and they are described by the Langmuir adsorption model. Potentiometric and spectroscopic (SEM/EDX, FTIR e XPS) analyses indicate that the biomass is bounded to the RE by oxygenated groups via ionexchange and complexation mechanisms... (Complete abstract click electronic access below)

O uso da energia nuclear para as mais diversas finalidades tem se intensificado e destacado pelos benefícios que proporciona. A medicina diagnóstica e terapêutica, a agricultura, a indústria, a geração de energia elétrica, são alguns exemplos. Entretanto, o uso da energia nuclear gera rejeitos radioativos e estes requerem tratamento adequado para garantir a segurança ambiental e dos seres vivos. A biossorção e bioacumulação representam uma alternativa emergente, para o tratamento de rejeitos radioativos líquidos, proporcionando redução de volume e mudança de estado físico. Este trabalho teve como objetivos estudar biossorventes para promover o tratamento de rejeitos líquidos contendo Amerício-241, proporcionando redução de volume e mudando seu estado físico para sólido. Os biossorventes avaliados foram: Saccharomyces cerevisiae imobilizadas em alginato de cálcio, Saccharomyces cerevisiae livres e inativadas, alginato de cálcio, Bacillus subtilis, Cupriavidus metallidurans e Ochrobactrum anthropi. Os resultados foram bastante satisfatórios, chegando a 100 % em alguns casos. Esta técnica parece viável para a implantação no Laboratório de Rejeitos Radioativos do IPEN - CNEN/SP a curto prazo, por ser simples e de baixo custo. / The use of nuclear energy for many different purposes has been intensified and highlighted by the benefits that it provides. Medical diagnosis and therapy, agriculture, industry and electricity generation are examples of its application. However, nuclear energy generates radioactive wastes that require suitable treatment ensuring life and environmental safety. Biosorption and bioaccumulation represent an emergent alternative for the treatment of radioactive liquid wastes, providing volume reduction and physical state change. This work aimed to study biosorbents for the treatment of radioactive liquid wastes contaminated with americium-241 in order to reduce the volume and change the physical state from liquid to solid. The biosorbents evaluated were Saccharomyces cerevisiae immobilized in calcium alginate beads, inactivated and free cells of Saccharomyces cerevisiae, calcium alginate beads, Bacillus subtilis, Cupriavidus metallidurans and Ochrobactrum anthropi. The results were quite satisfactory, achieving 100% in some cases. The technique presented in this work may be useful and viable for implementing at the Waste Management Laboratory of IPEN CNEN/SP in short term, since it is an easy and low cost method.

Rejeitos radioativos líquidos contendo compostos orgânicos precisam de atenção especial, porque os processos de tratamento disponíveis são caros e difíceis de serem gerenciados. A biossorção é uma potencial técnica de tratamento que tem sido estudada em rejeitos simulados. O termo biossorção é utilizado para descrever a remoção de metais, metalóides e/ou radionuclídeos por um material de origem biológica independentemente de sua atividade metabólica. Dentre as potenciais biomassas, os resíduos agrícolas apresentam características muito atraentes, pois possibilitam a remoção dos radionuclídeos presentes no rejeito utilizando um biossorvente de baixo custo. O objetivo deste estudo foi avaliar o uso potencial de diferentes biomassas originadas de produtos ou resíduos agrícolas (fibra de coco, casca de café e casca de arroz) no tratamento de rejeitos radioativos líquidos orgânicos reais. Foram realizados experimentos com essas biomassas incluindo i) Preparação, ativação e caracterização das biomassas; ii) Realização dos ensaios de biossorção e iii) Avaliação do produto da imobilização de biomassas em cimento. As biomassas foram testadas nas formas brutas e ativadas. A ativação foi realizada com soluções diluídas de HNO3 e NaOH. Os ensaios de biossorção foram realizados em frascos de polietileno, nos quais foram adicionados 10 mL do rejeito radioativo ou diluições do rejeito em água deionizada com o mesmo pH e 2 % da biomassa (m/v). No final do experimento, a biomassa foi separada por filtração e a concentração dos radioisótopos remanescente no filtrado foi determinada por ICP-OES e espectrometria gama. O rejeito estudado contém urânio natural (U (total)), amerício-241 e césio-137. Os tempos de contato adotados foram 30 min, 1, 2 e 4 horas e as concentrações estudadas variaram entre 10% e 100%. Os resultados foram avaliados por meio da capacidade máxima de sorção experimental e modelos ternários de isotermas e cinética. As maiores capacidades de sorção foram observadas com casca de café bruta, com valores aproximados de 2 mg/g de U (total), 40 x10-6 mg/g de Am-241 e 50 x10-9 mg/g de Cs-137 e, também, com fibra de coco ativada, com valores de 2 mg/g de U (total), 70 x10-6 mg/g de Am-241 e 40 x10-9 mg/g de Cs-137. As propriedades avaliadas na determinação da qualidade do produto de imobilização foram água livre, resistência mecânica, trabalhabilidade e tempo de pega. Os melhores produtos de imobilização para estas biomassas foram obtidos com uma relação água/cimento de 0,30, contendo 5%, 10% e 15% de casca café bruto, fibra de coco ativada e casca de café ativado, respectivamente. Estes resultados sugerem que a biossorção com casca de café bruta e fibra de coco sob a forma ativada podem ser aplicadas no tratamento de rejeitos radioativos líquidos orgânicos contendo urânio, amerício-241 e césio-137. / Radioactive liquid waste containing organic compounds need special attention, because the treatment processes available are expensive and difficult to manage. The biosorption is a potential treatment technique that has been studied in simulated wastes. The biosorption term is used to describe the removal of metals, non-metals and/or radionuclides by a material from a biological source, regardless of its metabolic activity. Among the potential biomass, agricultural residues have very attractive features, as they allow for the removal of radionuclides present in the waste using a low cost biosorbent. The aim of this study was to evaluate the potential use of different biomass originating from agricultural products (coconut fiber, coffee husk and rice husk) in the treatment of real radioactive liquid organic waste. Experiments with these biomasses were made including i) Preparation, activation and characterization of biomasses; ii) Conducting biosorption assays; and iii) Evaluation of the product of immobilization of biomasses in cement. The biomasses were tested in raw and activated forms. The activation was carried out with diluted HNO3 and NaOH solutions. Biosorption assays were performed in polyethylene bottles, in which were added 10 mL of radioactive waste or waste dilutions in deionized water with the same pH and 2% of the biomass (w/v). At the end of the experiment, the biomass was separated by filtration and the remaining concentration of radioisotopes in the filtrate was determined by ICP-OES and gamma spectrometry. The studied waste contains natural uranium, americium-241 and cesium-137. The adopted contact times were 30 min, 1, 2 and 4 hours and the concentrations tested ranged between 10% and 100%. The results were evaluated by maximum experimental sorption capacity and isotherm and kinetics ternary models. The highest sorption capacity was observed with raw coffee husk, with approximate values of 2 mg/g of U (total), 40 x10-6 mg/g of Am-241 and 50 x10-9 mg/g of Cs-137 and, also, with activated coconut fiber, with values of 2 mg/g of U (total), 70 x10-6 mg/g of Am-241 and 40 x10-9 mg/g of Cs-137. The properties evaluated to determine the quality of the immobilization product were free water, mechanical strength, workability and setting time. The best immobilization products for these biomasses were obtained with a water/cement ratio of 0.30, containing 5%, 10% and 15% of raw coffee husk, activated coconut fiber and activated raw coffee husk, respectively. These results suggest that biosorption with raw coffee husk and activated coconut fiber can be applied in the treatment of radioactive liquid organic wastes containing uranium, americium-241 and cesium-137.

Neste trabalho é apresentado o potencial de remoção de íons estrôncio de soluções aquosas pelas fibras de coco na forma bruta e na forma ativada com peróxido de hidrogênio, 1% e 4%, em meio básico. Os experimentos de biossorção foram realizados em batelada com 2 mg.L-1 de solução de Sr(NO3)2 e foram estudadas as influências dos seguintes parâmetros: tempo de contato, pH e a eficiência de biossorção das fibras ativadas em comparação com a fibra de coco bruta (FCB). A caracterização das fibras antes e após o tratamento, e a presença de Sr2+ nas fibras foram realizadas por microscopia de varredura eletrônica com detector de espectroscopia de energia dispersiva, espectroscopia de difração de raios X, espectroscopia de infravermelho e por análise térmica. Dentre as fibras estudadas, a fibra de coco ativada com 1% H2O2 (FCA 1) apresentou a maior capacidade de biossorção: 3,6 mg.g-1, nas seguintes condições: 5 mg de biomassa em pH 6, após 90 minutos de tempo de contato à temperatura ambiente. A fibra de coco ativada com 4% H2O2 (FCA 2) levou a uma maior degradação dos constituintes da fibra e consequentemente a uma menor remoção de íons de Sr2+.Para os estudos de modelos de isotermas de biossorção de Sr2+, tanto a FCB quanto a FCA 1 ajustaram-se melhor ao modelo de Langmuir e à cinética de pseudo-segunda ordem. Os parâmetros termodinâmicos energia livre de Gibbs (ΔG) e coeficiente de distribuição (KD) foram -0,90 kJ.mol-1 e 265,3L.Kg-1 para a FCB e de -7,2 kJ.mol-1 e 824,3 L.Kg-1 para a FCA1. Esses resultados demonstraram que a FCA 1 possui uma boa eficiência para remover íons de Sr2+de resíduos químicos aquosos e é uma boa alternativa no tratamento de rejeitos radioativos líquidos contendo íons 90Sr. / This work presents the potential of strontium ions removal from aqueous solutions using coconut fiber in raw and treated form with hydrogen peroxide, 1% and 4%, in alkaline conditions. The biosorption experiments were performed in batch mode with 2 mg.L-1 solution of Sr(NO3)2 and the influence of the following parameters were studied: contact time and pH. It was also evaluate the biosorption efficiency of the treated coconut fibers in comparison with the raw coconut fiber (RCF). The fibers characterizations before and after treatment and the presence of the Sr2+ in the fibers were performed by scanning electron microscopy with a detector energy dispersive spectroscopy, diffraction of x-ray spectroscopy, infrared spectroscopy and thermal analysis. Among the studied fibers, the treated coconut fiber with 1% of H2O2 (TCF 1) showed the major biosorption capacity of 3.6 mg.g-1 in the following conditions: 5 mg of biomass at pH 6, 90 minutes of contact time at room temperature. Treated coconut fiber with 4% H2O2 (TCF 2) showed the lowest Sr2+ ions removal due to degradation of the fibers constituents. For studies of biosorption isotherms, both raw and treated coconut fiber (TCF 1) were fitted better to Langmuir model and the kinetics reaction was of pseudo-second order. The thermodynamic parameters Gibbs free energy (ΔG) and distribution coefficient (KD) were -0.90 kJ.mol-1 and 265.3 L.Kg-1 for RCF and of -7,2 kJ.mol-1 and 824.3L.Kg-1 for TCF 1. These results demonstrated that the TCF 1 has good efficiency for removing Sr2+ ions in the aqueous chemical waste and is a good alternative in treatment of liquid radioactive wastes containing 90Sr.

Vaal University of Technology / ii Abstract The use of biosorption to complement conventional water treatment techniques has gained widespread appeal partly due to the abundance of waste materials that can be used as low cost biosorbents. However, some materials have not yet been exploited in this regard. This research was aimed at evaluating the biosorption potential of Mangifera indica (mango) seed shells that are readily available in several farming areas of the Limpopo and Mpumalanga Provinces of South Africa. In this work, powdered ethylenediaminetetraacetic acid (EDTA) functionalized biosorbent was prepared from alkali treated biomass of waste mango seed shells. The influence of alkali treatment and EDTA functionalization on the physicochemical properties of the biomass was characterized using Fourier transform infra-red spectroscopy, X-ray diffraction and thermogravimetric analysis. Results confirmed removal of hemicelluloses, conversion of crystalline to amorphous cellulose and the introduction of carboxyl, ester and tertiary amine groups from EDTA. Furthermore, the powdered biosorbent was immobilized using calcium alginate for adaptation to column sorption. The powdered biosorbents were tested for sorption of lead(II) ions using batch sorption experiment. Through EDTA functionalization, improvement in sorption capacity for lead(II) ions from 59.25 mg.g-1 to 306.33 mg.g-1 was realized. The Langmuir and Pseudo-nth order models most suitably simulated the equilibrium and kinetics of sorption by both functionalized and non-functionalized biomaterials. The calcium alginate immobilized biosorbent was evaluated for non-specific sorption of ionic species of copper, chromium, nickel and iron from electroplating wastewater through discontinuous column sorption experiments. Highest copper, chromium, nickel and iron removal was 12.3%, 14.8%, 4.4% and 13.8% from nonacidified samples at an initial pH of 3.4, and 15.5%, 18.7%, 13.7% and 17.3% from samples acidified to an initial pH of 1.8. Repeated sorption-desorption cycles involving acidified wastewater resulted in successive improvement in metal uptake against declining recovery indicating irreversible binding on –COOH groups formed from –CH2OH groups through a redox reaction involving reduction of chromium(VI) to chromium(III). Keywords: Mangifera indica; biosorption; alkali treatment; carboxyl functionalization; calcium alginate

This Ph. D. thesis presents results and conclusions from studies 1) investigating the interaction between metal and metalloid ions and thermophilic bacteria, and 2) characterizing microbial populations in a geothermally active habitat with relatively high concentrations of metalloid ions and compounds. In initial cadmium ion toxicity assays, the minimal inhibition concentration for 46 thermophilic bacteria of the genera Aneurinibacillus, Anoxybacillus, Bacillus, Brevibacillus, Geobacillus, and Thermus were determined. The highest tolerances to cadmium ions (Cd2+) in the range of 400 to 3200 micro;M were observed for species belonging to the genus Geobacillus. The thermophilic Gram-positive bacteria Geobacillus stearothermophilus and G. thermocatenulatus were selected to describe further biosorption reactions between cadmium ions and chemically reactive functional groups (potential ligands) within and onto the bacterial cell walls. Data obtained from electrophoretic mobility, potentiometric titration and cadmium ion adsorption experiments were used to quantify the number and concentrations of ligands and to determine the thermodynamic stability constants for the ligand-cation complexes. The first reported surface complexation models (SCMs) quantifying metal ion adsorption by thermophilic microorganisms predicted cadmium adsorption and desorption by both studied Geobacillus strains over a range of pH values and for different biomasses. The results indicated the functional group, with a deprotonation constant pK value of approximately 3.8, to be more dominant in cation biosorption accounting for 66 and 80% of all titrable groups for G. thermocatenulatus and G. stearothermophilus, respectively. The generated SCMs are different from model parameters obtained from mesophilic species that have been studied to date and might indicate a different biosorption behavior for both studied Geobacillus strains. Another objective of this thesis was to characterize microbial populations in the hot spring Champagne Pool, located in Waiotapu, New Zealand. The thermal spring is approximately 65 m in diameter and discharges water at 75eg; C and pH 5.5, which is oversaturated with arsenic and antimony compounds that precipitate and form orange deposits. Recovered nucleic acids and adenosine 5'-triphosphate (ATP) concentrations obtained for Champagne Pool water samples indicated low microbial density and were in good agreement with relatively low cell numbers of 5.6 plusmn; 0.5 x10^6 cells per ml. Denaturing gradient gel electrophoresis (DGGE) and 16S rRNA gene clone library analyses revealed the abundance of Sulfurihydrogenibium, Sulfolobus and Thermofilum-like populations in Champagne Pool. Two novel bacteria and one novel archaeon were successfully isolated with a distant phylogenetic relationship to Sulfurihydrogenibium, Thermoanaerobacter, and Thermococcus, respectively. Genotypic and metabolic characteristics differentiated isolate CP.B2 from described species of the genus Sulfurihydrogenibium. CP.B2 represents a novel genus within the Aquificales order, for which the name Venenivibrio stagnispumantis gen. nov., sp. nov. is proposed. V. stagnispumantis is a thermophilic, chemolithothrophic bacterium, that utilizes molecular hydrogen as electron donor and oxygen as electron acceptor and displayed growth in the presence of up to 8 mM NaAsO2 (As3+) and more than 20 mM Na2HAsO4.7H2O (As5+). However, growth was not observed when Na2HAsO4.7H2O and NaAsO2 were provided as the sole electron acceptor and donor pair. Arsenic resistance was conferred by the genes arsA and arsB

Perfluorooctane sulfonate (PFOS) and related perfluoroalkyl surfactants (PFAS) are ubiquitous contaminants of increasing public concern due to their environmental persistence, toxicity, and bioaccumulation. These perfluorinated compounds have been used for more than half a century in a wide variety of industrial and consumer products ranging from stain repellents such as Teflon® to aqueous fire-fighting foams and to grease-proof food packing. The public health and environmental risks posed by PFAS have driven environmental agencies and the industry to restrict their use to specific applications where they cannot be replaced by other chemicals. The sources and pathways of PFOS and its derivatives in the environment are not well understood. Analysis of environmental samples is critical to understand the fate, transport and persistence of these emerging contaminants. Techniques based on fluorine nuclear magnetic resonance (¹⁹F NMR) spectroscopy and high performance liquid chromatography (HPLC) with suppressed conductivity detection were successfully developed to monitor the presence of PFAS in water samples. Chromatographic separation of C₄ to C₈ PFAS surfactants was achieved using a C₁₈ reversed-phase column and a mobile phase consisting of a mixture of boric acid and acetonitrile at mixing ratios ranging from 75:25 to 45:55 (v/v). The combination of these two techniques was very effective for characterization and routine quantification of PFOS and related chemicals. Analytical methods based on ¹⁹F NMR, HPLC-suppressed conductivity detection, and liquid chromatography with tandem mass spectrometry (LC-MS/MS) were employed to characterize commercial PFOS samples. Linear and branched PFOS isomers in a percentage ratio of 75:25 were identified. Municipal wastewater treatment systems are one of the major sources of PFAS emissions into the environment. The presence of PFAS in sewage sludge from two wastewater treatment plants in Tucson, Arizona, was investigated. Sludge samples were washed with acetic acid and extracted with a mixture of acetic acid and methanol. The extract was cleaned and concentrated by means of solid phase extraction. LC-MS/MS operating in the selective ion monitoring (SIM) mode was employed to assess the presence of perfluorosulfonates, perfluorosulfonamides, and perfluorocarboxylates in sewage sludge samples. PFOS was the only perfluoroalkyl chemical detected in municipal sludge samples at a concentration of 77 ± 5 g kg⁻¹ sludge dry weight. Cost-effective treatment techniques for removing PFAS from industrial effluents are needed to minimize discharges of these pollutants. Reductive dehalogenation is widely applied to the degradation of highly chlorinated compounds. Hence, the susceptibility of PFOS and related compounds to biological and chemical reductive dehalogenation was evaluated in batch assays. PFAS were not reductively dehalogenated by different microbial consortia even after periods of incubation exceeding 2 y, confirming the high resistance of these compounds to microbial degradation. The anaerobic biodegradability of PFOS and perfluorobutane sulfonate (PFBS) samples exposed to electrochemical pretreatment with boron-doped diamond film electrodes was also investigated. The oxidation decreased the concentration of PFAS and dissolved organic carbon in solution, confirming the destruction of these compounds. However, the oxidative treatment did not enhance the susceptibility of PFAS to microbial degradation even after extended periods of incubation (> 1 y). In contrast, PFOS was reductively dehalogenated with a biomimetic system based on vitamin B12 as the catalyst and Ti(III) citrate as the reducing agent. The optimal treatments conditions of the reaction were 260 μM vitamin B₁₂, 36 mM Ti(III) citrate, 70°C and solution pH 9.0. Interestingly, branched PFOS isomers were more prone to degradation by vitamin B₁₂ catalysis compared to the linear isomer. Removal of 3 mol Fper mol of technical PFOS and 12 mol F- per mol of branched PFOS isomers was achieved. Defluorination of PFOS was also observed at environmental relevant conditions of 30°C and pH 7.0, albeit at lower degradation rates. Fluoride and carbon dioxide were identified as the major products of the chemical defluorination. Traces of partially fluorinated volatile compounds were also detected in the headspace. The feasibility of removing PFAS compounds from aqueous streams by sorption onto granular activated carbon (GAC), zeolite, and wastewater treatment sludge was examined in batch isotherm experiments. The fluorocarbon chain and the functional group influenced sorption of the anionic surfactants, PFOS adsorbed more strongly to GAC than perfluorooctanoic acid (PFOA) and PFBS. Activated carbon showed the highest affinity for PFOS (Freundlich K(F) values of 36.7 to 60.9) followed by the hydrophobic, high-silica zeolite NaY (Si/Al 80, K(F) of 31.8) and lastly anaerobic sludge (K(F) of 0.95 to 1.85). GAC sorption is a suitable treatment for the removal of anionic perfluoroalkyl surfactants when present at low concentrations. Fluoride has been identified as the major product of the reductive dehalogenation of PFOS and derivatives. Thus, the toxicity of inorganic fluoride towards the main microbial populations responsible for the removal of organic constituents and nutrients in wastewater treatment processes was also studied. Fluoride concentrations ranging from 18 to 43 mg L⁻¹ caused 50% inhibition (IC₅₀) of the activity of propionate- and butyratedegrading microorganisms and of acetate-utilization by methanogens evaluated under mesophilic and thermophilic conditions. All other microbial populations evaluated in this study, i.e., glucose fermenters, aerobic glucose-degrading heterotrophs, denitrifying bacteria, and H₂-utilizing methanogens tolerated fluoride at very high concentrations (> 500 mg L⁻¹). In the same manner, H₂-utilizing methanogens also tolerated PFOS and PFBS at concentrations as high as 200 and 500 mg L⁻¹, respectively.