Made available in DSpace on 2016-08-19T12:56:35Z (GMT). No. of bitstreams: 1 THAIS_ FRAZAO_ PINTO.pdf: 809423 bytes, checksum: b8458673c3339f802bd73fe54560bb20 (MD5) Previous issue date: 2010-08-02 / This work treated of modified wood sawdust with succinic anhydride and your application as adsorbent for remazol brilliant violet 5R (VR5) textile dye. The new material obtained was designated SMAS. The vibrations spectra indicated the presence of oxygenated groups, being the modification confirmed by Infrared, 13C NMR spectroscopy and titration of acid groups that indicated the introduction of carboxylic groups the material. It was found that the material can act as adsorbent to dye investigated and your active sites further enriched, due to considerably increased the adsorption capacity compared to natural material. Furthermore, the process of adsorption proved to be highly dependent of the pH and the largest amount adsorbed was obtained at pH 2.0. The adsorption of remazol brilliant violet 5R textile dye by wood sawdust modified with succinic anhydride followed the kinetic modeling of second order and was well described by the Freundlich model. In the conditions studied was reached a percentage of removal 51.66%. / Este trabalho tratou da modificação de serragem de madeira por anidrido succínico e sua aplicação como adsorvente para o corante têxtil violeta brilhante 5R remazol (VR5). O novo material obtido foi denominado SMAS. Os espectros vibracionais indicaram a presença de grupos oxigenados, sendo a modificação comprovada a partir de Infravermelho, RMN de 13C e da titulação dos grupos ácidos, que indicaram a inserção de grupos carboxílicos ao material. Verificou-se que o material pode atuar como adsorvente para o corante investigado e que houve um acréscimo no número de sítios ativos, pois aumentou consideravelmente a capacidade de adsorção frente ao corante, comparado ao material in natura. Além disso, o processo de adsorção se mostrou fortemente dependente do pH e a maior quantidade adsorvida foi obtida em pH 2,0. A adsorção do corante Violeta Remazol 5R por serragem de madeira quimicamente modificada com anidrido succínico seguiu a modelagem cinética de segunda ordem e foi bem descrita pelo modelo de Freundlich. Nas condições estudadas, alcançou-se uma porcentagem de remoção de 51,66 %.

Remoções quase totais de clorofenóis, por processos anaeróbios, já foram atingidas mediante elevada concentração de matéria orgânica e um número considerável de fontes de carbono. Porém, é necessário que se investigue o desempenho dos reatores submetidos a condições menos idealizadas. Este trabalho apresenta o desenvolvimento de uma metodologia para avaliar um reator anaeróbio de leito fluidificado (RALF) como etapa de pré-tratamento de substrato sintético contendo pentaclorofenol (PCP). Para isso, foram adotadas as seguintes condições experimentais: fonte única de carbono; concentração reduzida de matéria orgânica; biomassa não previamente adaptada, e menores tempos de detenção hidráulica. Para cumprir o objetivo citado, foram desenvolvidos dois reatores, com 2,2 e 16 litros, respectivamente, e foram realizadas etapas de avaliação de materiais suporte, estudo de diversas interações (partícula/fluido, partículas fluido, biopartícula/fluido e biopartículas/fluido), e análise do desempenho do RALF sem PCP e com PCP. Os materiais suporte escolhidos foram a alumina, o basalto e o carvão ativado granular, todos com diâmetros próximos a 3 mm. Eles foram avaliados em ensaios de caracterização física, de microscopia eletrônica de varredura, de fluidodinâmica e de análise de imagens. O carvão apresentou os melhores resultados e foi escolhido para a continuidade do trabalho. As interações foram analisadas através de ensaios fluidodinâmicos, isotermas de adsorção, dentre outros. Nas condições experimentais utilizadas, a biomassa aumentou a densidade da partícula, fato que foi comprovado pelos ensaios para determinação da velocidade mínima de fluidificação, de expansão e porosidade do leito, e também de velocidade terminal da partícula isolada. As isotermas de adsorção demonstraram que a presença de matéria orgânica diminuiu em 9% a adsorção do PCP. O RALF apresentou um comportamento satisfatório no período de operação sem PCP. Nos 105 dias de operação, a eficiência média de remoção de DQO ficou quase sempre superior a 90%, e os outros parâmetros de monitoramento de desempenho apresentaram valores típicos, indicando estabilidade no processo. A presença de PCP no sistema, nas concentrações utilizadas, não alterou a qualidade da biomassa presente, e nem os parâmetros de monitoramento de desempenho, como DQO, alcalinidade, pH e ácidos voláteis. Mesmo sob condições menos idealizadas, foi observado um desempenho satisfatório do reator na remoção do PCP. Em concentrações variando de 1 a 6 mg/L, foram observadas eficiências médias de remoção de 93% e 70%, respectivamente, para os 80 dias de operação nessas condições. Diante dos resultados obtidos, foi possível concluir que a remoção de PCP em um RALF pode ser atingida mediante condições operacionais mais simples. / The almost total removal of chlorophenols by anaerobic processes has been achieved under high concentrations of organic matter and a considerably large number of carbon sources. However, it is necessary to investigate the performance of such reactors under less idealized conditions. The present work shows the development of a new methodology for evaluating the use of an anaerobic fluidized bed reactor (AFBR) in the pretreatment step of a synthetic substrate containing pentachlorophenol (PCP). In order to do that, the following experimental conditions were used: a single source of carbon; reduced concentrations of organic matter; non-previously adapted biomass, and smaller hydraulic retention times. To achieve the main objective, two reactors, one having a volume of 2.2 L and the other one, 16 L, were especially designed; evaluation steps of support material and the study of several interactions (particle/fluid, particles/fluid, bioparticle/fluid, bioparticles/fluid) were carried out, and the performance of the AFBR with and without PCP was analyzed. The three support materials employed were alumina, basalt and granular activated carbon, all having average diameters of 3 mm. These materials were evaluated through physical characterization methods, microscopy, hydrodynamic and image analyses. The activated coal showed the best results and was exclusively employed in the remainder of the work. The interactions were analyzed by hydrodynamics and adsorption isotherms, to name but a few. Under the experimental conditions employed, the biomass made the particle density increase, a fact that was verified in the determination of the minimum fluidization velocity, the bed porosity and expansion as well as the terminal velocity of isolated particles. The adsorption isotherms showed a decrease of 9% in PCP absorption due to the existence of organic matter. The AFBR showed satisfactory results during the operation without PCP. In the 105 days of operation, the average efficiency of COD removal remained almost always over 90%, while the other performance monitoring parameters remained at typical values, indicating the process stability. The presence of PCP under the concentrations used in the system did not seem to affect neither the quality of the biomass nor the performance monitoring parameters, like COD, alkalinity, pH and volatile acids. Even under less idealized conditions, the reactor showed good performance in removing PCP. The average efficiencies of removal attained around 93% and 70% for concentrations of 1 to 6 mg/L respectively. These concentration levels were kept during 80 days. In view of the results obtained, it is possible to conclude that reasonably good efficiency of PCP removal in AFBR can be attained under simpler operational conditions.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-03-07T14:00:16Z No. of bitstreams: 1 victorwegnermaus.pdf: 6204787 bytes, checksum: 1c441ace80fd21b15887daa548beac3e (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-03-07T15:06:37Z (GMT) No. of bitstreams: 1 victorwegnermaus.pdf: 6204787 bytes, checksum: 1c441ace80fd21b15887daa548beac3e (MD5) / Made available in DSpace on 2017-03-07T15:06:37Z (GMT). No. of bitstreams: 1 victorwegnermaus.pdf: 6204787 bytes, checksum: 1c441ace80fd21b15887daa548beac3e (MD5) Previous issue date: 2011-02-24 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Águas subterrâneas são econômica e socialmente importantes e sua contaminação gera grandes preocupações. Nesse sentido a modelagem computacional pode contribuir na gestão de águas subterrâneas e no planejamento da remediação de áreas contaminadas, realizando previsões considerando implicações de diversas alternativas sem o custo de esperar ou colocá-las em prática. O objetivo deste trabalho é estudar modelos matemáticos para os fenômenos envolvidos bem como desenvolver ferramentas numéricas para a simulação computacional que podem auxiliar na prevenção, no controle e na remediação da poluição das águas subterrâneas. Nos experimentos computacionais é simulado o transporte de múltiplas espécies. O problema corresponde a um sistema de equações diferenciais parciais não lineares de advecção-difusão-reação, acopladas pelas reações de biodegradação e sorção em modo de não equilíbrio. A biodegradação é representada pelo modelo cinético de Monod multiplicativo. A sorção, descrita pela isoterma de Freundlich, atua em modo de equilíbrio e não equilíbrio simultaneamente, e ocorre apenas sobre o contaminante. A solução do sistema de EDP’s é obtida em dois passos. No primeiro resolve-se o transporte do contaminante e do oxigênio, onde a discretização espacial é realizada pelo método dos elementos finitos e um método da família trapezoidal generalizada para a discretização temporal. O método de Newton é utilizado para tratar a não linearidade gerada pela sorção de equilíbrio no transporte do contaminante. No passo seguinte, as reações são aproximadas pontualmente pelo método de Runge-Kutta de quarta ordem. Os resultados obtidos nos experimentos computacionais são comparados aos resultados de simulações encontradas na literatura. Nas simulações observou-se a influência da inclusão das reações não lineares de biodegradação e sorção de equilíbrio e não equilíbrio ocorrendo simultaneamente. Assim o estudo das interações entre as reações, pode trazer contribuições para a modelagem do transporte de contaminantes em águas subterrâneas. / Groundwater contamination generates large concern related with public health and environmental conservation. The computational modeling can contribute to groundwater management and remediation planning of contaminated areas, making predictions for several scenarios of contamination without the cost of waiting or of putting them into practice. The aim this work is study mathematical models for the phenomena involved and develop numerical tools for the simulation that can assist in the prevention, control and remediation of groundwater pollution. In the computational experiments is simulated the multiple species transport. This problem is modeled for a system of nonlinear partial differential equations, coupled by the biodegradation and sorption reactions. Biodegradation is represented by the multiplicative Monod kinetic model. The sorption is described by the Freundlich isotherm and occur only with the contaminant. The solution of the PDE’s sistem is obtained in two steps. In the first resolves the contaminant and oxygen transport, the finite elements method and Crank-Nicolson scheme are respectively used in the spatial and time discretizations. The Newton method is used to treat the nonlinearity generated by the sorption equilibrium in the transport of the contaminant. The ordinary differential equations of the reactions is approximated by the fourth-order Runge- Kutta method. Numerical results presented in this work have shown good agreement with solutions introduced by others authors. In the simulations we observed the influence of the inclusion of non-linear reactions of biodegradation and sorption equilibrium and nonequilibrium happening simultaneously. So the study of interactions between the reactions should contribute to the modeling of contaminant transport in groundwater.

Les travaux de thèse ont porté sur la synthèse d’un MIP (polymère à empreintes moléculaires) spécifique d’un fongicide se trouvant dans la majorité des vins français : l’iprodione. Pour extraire l’iprodione à partir du vin, un challenge important se présentait : le milieu hydroalcoolique est un solvant dipolaire alors que l’interaction du MIP avec l’iprodione se base sur des interactions dipôle-dipôle. Les premières études d’extraction de l’iprodione ont été faites sur un MIP obtenu par polymérisation en masse à partir du méthacrylamide et de l'éthylène glycol diméthacrylate (EGDMA). Le MIP était plus efficace que le NIP (polymère non imprimé) dans des solutions hydroalcooliques ce qui vérifie que l’impression moléculaire était réussie. Un plan d’expériences 23 a été appliqué pour étudier l’influence de 3 facteurs de synthèse de MIP (la méthode de polymérisation, la nature de l'agent réticulant et le type de monomère fonctionnel) sur les propriétés de reconnaissance des polymères vis-à-vis de l’iprodione. 8 MIP et 8 NIP ont été ainsi synthétisés. Les isothermes d'adsorption de l'eau et de l’iprodione par les MIPs et les NIPs ont été déterminées. Des différences significatives entre les polymères ont été mises en évidences impliquant une relation entre l’adsorption de l’eau et l’adsorption de l’iprodione. La formation des empreintes moléculaires au sein des MIP a été démontrée par plusieurs techniques comme la calorimétrie différentielle à balayage et la résonance magnétique nucléaire. Les meilleures propriétés de reconnaissance de l’iprodione sont obtenues avec le MIP synthétisé par précipitation à partir du méthacrylamide comme monomère fonctionnel et de l’EGDMA comme réticulant. Ce MIP a été utilisé en extraction en phase solide (SPE) pour la pré-concentration de l’iprodione dans un vin blanc avec un facteur de pré-concentration égal à 6 et sa sélectivité par rapport à deux fongicides : le pyriméthanil et le procymidone a été démontrée. / The aim of this study was the synthesis of a MIP (molecularly imprinted polymer) specific for a fungicide that is found in the majority of the french wine: iprodione. The challenge for extracting iprodione from wine medium was that the hydoralcoholic solution is a dipolar solvent, whereas the interaction between the MIP and iprodione is based on dipolar interactions. The first extraction study of iprodione was made on a MIP synthesized by bulk polymerization using methacrylamide and ethylene glycol dimethacrylate (EGDMA). The MIP was found to be more efficient than the NIP (non-imprinted polymer) in hydroalcoholic solutions which demonstrates that the molecular imprinting was successful. Then we synthesized 8 MIPs and 8 NIPs following an 23 experimental design in order to study the influence of three synthesis factors (the polymerization method, the nature of the crosslinker and the type of the functional monomer) on the iprodione recognition properties of the polymers. The water and the iprodione adsorption isotherms for MIPs and NIPs were determined. The result showed significant differences between the polymers involving a relationship between the water adsorption and the adsorption of iprodione. The molecular imprinting has been demonstrated by several techniques such as the differential scanning calorimetry and the nuclear magnetic resonance. The best recognition properties of iprodione are obtained with the MIP which was synthesized by precipitation polymerization using methacrylamide as functional momonomer and EGDMA as crosslinker. This MIP was used in solid phase extraction (SPE) for pre-concentration of iprodione in a white wine with a pre-concentration factor of 6. Its selectivity versus two fungicides: procymidone and pyrimethanil has been demonstrated.

The normal operation of the endocrine (hormonal) system can be disrupted by a number of man-made and naturally-occurring chemicals, thereby affecting those physiological processes that are under hormonal control. Such substances are called endocrine disrupting compounds (EDCs). The endocrine disruption issue has alarmed the environmental authorities since the substances involved can hinder hormonal processes causing far-reaching effects on reproduction and development in current and future human and wildlife generations. Effects on some species of fish triggered worldwide concern and initiated a research scheme which is being undertaken by various organisations e.g. United States Environmental Protection Agency (USEPA), United Kingdom Environment Agency (UKEA), Oslo and Paris Commission (OSPAR), Japan Environment Agency (JEA) and World Wildlife Fund (WWF) in order to assess the effects (present and potential), point of generation, levels of contamination and exposure limits. The findings showed that most of the oestrogens are produced by humans and animals and get discharged into river streams mainly through sewage effluents. Fish in particular have been found to be affected the most even when the oestrogenic levels in water are very low. The probability of future European legislation to eliminate hormonally active compounds from wastewaters suggests that new and alternative methods should be developed for their removal. In this work, the adsorption of 17ß-oestradiol (E2) and 17a-ethinyl oestradiol (EE2) onto several granular activated carbons and Hypersol-Macronet hypercrosslinked polymers was investigated by batch experiments after a low level detection system had been developed using Gas Chromatography Mass Spectrometry (GC/MS). Equilibrium experiments were carried out for all adsorbents to quantify the sorption capacity for E2 and EE2. For better assessment of the sorbents performance, their physical properties such as surface area, average pore diameter and micropore volume and chemical structure were characterised by N2 adsorption experiments, scanning electron microscopy (SEM), FTIR spectroscopy, elemental analysis, sodium capacity determination, pH titration, proton binding curves and zeta potential measurements. Adsorption isotherm data were fitted to the Langmuir and Freundlich equations. Activated carbons were found to be preferable to Hypersol-Macronet hypercrosslinked polymers for adsorption purposes. The adsorption of oestrogens appears to be controlled by hydrophobic interactions. Kinetic experiments were performed with different size ranges of adsorbents at different concentrations and the results were analysed by a particle diffusion model. It was found that concentration did not seem to influence the kinetics of the oestrogen sorption whereas the particle size of the adsorbents influenced the adsorption rate of both molecules. The particle diffusion model seemed to fit the data collected for the adsorption rate of 17B-oestradiool onto the adsorbents but gave a poor fit for most of the data collected for 17a-ethinyl oestradiol.

La durabilité des structures en béton armé ainsi que leur durée de vie sont étroitement liées à la mise en œuvre simultanée de nombreux phénomènes physiques et chimiques. Ceux-ci sont de diverses natures mais restent, en général, fonction des propriétés hydriques des matériaux étudiés. Ainsi, la prédiction des dégradations potentielles d'un matériau cimentaire requiert l'étude du transport de l'eau liquide et des phases gazeuses à travers ce dernier, considéré comme un milieu poreux. En milieu naturel, les structures subissent des variations périodiques de l'humidité relative extérieure (HR). Cependant, la plupart des modèles de transfert hydrique préexistants dans la littérature, s'intéresse uniquement au processus de séchage. Il existe peu de modèles décrivant à la fois l'humidification et le séchage du matériau (ces deux phénomènes se produisent dans le matériau en condition naturelle d'humidité relative (HR)). Tenir compte des phénomènes d'hystérésis dans les transferts hydriques réduit à nouveau le nombre de modèles à disposition. Ainsi, cette thèse s'attache à proposer une meilleure compréhension de l'état hydrique du béton en fonction des variations d'humidité relative extérieure, sur la base d'une nouvelle campagne expérimentale et de modélisations numériques. Un soin sera apporté afin de tenir compte dans les modèles numériques des effets d'hystérésis. Dans ce travail, nous détaillerons, tout d'abord, un modèle multi-phasiques complet. Un modèle simplifié est obtenu, sur la base de considérations théoriques et de vérifications expérimentales dans le cas où la perméabilité intrinsèque à l'eau liquide reste très inférieure à la perméabilité intrinsèque au gaz. Une étude comparative des modèles d'hystérésis couramment utilisés permet d'obtenir un jeu de modèles proposant les meilleures prédictions d'isothermes de sorption d'eau et de leurs hystérésis. Par la suite, le modèle de transport simplifié est couplé avec les modèles d'hystérésis sélectionnés afin de simuler les transferts hydriques dans des bétons soumis à des cycles d'humidification-séchage. La comparaison avec des données expérimentales révèle que la prise en compte de l'hystérésis de l'isotherme de sorption d'eau ne peut pas être négligé. De plus, il est montré que les prédictions obtenues avec des modèles d'hystérésis théoriques, sont les plus cohérentes avec les résultats expérimentaux, en particulier, pour des chemins secondaires d'hystérésis. Plusieurs scénarios (conditions environnementales, bétons différents) sont également simulés. Les résultats obtenus pointent à nouveau la nécessité de tenir compte de l'hystérésis lors de la modélisation des transferts hydriques à travers des matériaux cimentaires soumis à des variations d'humidité relative. La définition d'une profondeur pour laquelle le profil hydrique du béton est modifié par les variations périodiques d'humidité relative permet de mieux comprendre comment la modélisation de la pénétration des espèces ioniques est influencée par les cycles d'humidification-séchage. Par ailleurs, notre analyse révèle qu'il est pertinent de considérer l'effet de Knudsen pour la diffusion de la vapeur afin d'améliorer la prédiction de la diffusivité apparente / The durability of reinforced concrete structures and their service life are closely related to the simultaneous occurrence of many physical and chemical phenomena. These phenomena are diverse in nature, but in common they are dependent on the moisture properties of the material. Therefore, the prediction of the potential degradation of cementitious materials requires the study of the movement of liquid-water and gas-phase transport in the material which is considered as a porous medium. In natural environment, structures are always affected by periodic variations of external relative humidity (RH). However, most moisture transport models in the literature only focus on the drying process. There are few researches considering both drying and wetting, although these conditions represent natural RH variations. Even few studies take into account hysteresis in moisture transport. Thus, this work is devoted to better understand how the moisture behaviour within cementitious materials responds to the ambient RH changes through both experimental investigations and numerical modelling. In particular, hysteretic effects will be included in numerical modelling. In this thesis, we first recalled a complicate multi-phase continuum model. By theoretical analysis and experimental verification, a simplified model can be obtained for the case of that the intrinsic permeability to liquid-water is smaller than the intrinsic permeability to gas-phase. The review of commonly-used hysteresis models enabled to conclude a set of best models for the prediction of water vapour sorption isotherms and their hysteresis. After that, the simplified model was coupled with selected hysteresis models to simulate moisture transport under drying and wetting cycles. Compared with experimental data, numerical simulations revealed that modelling with hysteretic effects can provide much better results than non-hysteresis modelling. Among different hysteresis models, results showed that the use of the conceptual hysteresis model, which presents closed form scanning loops, can provide more accuracy predictions. Further simulations for different scenarios were also performed. All comparisons and investigations enhanced the necessity of considering hysteresis to model moisture transport for varying relative humidity at the boundary. The investigation of moisture penetration depth could provide a better understanding of how deep moisture as well as ions can move into the material. Furthermore, the analysis revealed that the consideration of Knudsen effects for diffusion of vapour can improve the prediction of the apparent diffusivity

Orientador: Newton Luiz Dias Filho / Banca: Andre Henrique Rosa / Banca: Wagner Luís Polito / Resumo: A combinação de diferentes tipos de materiais para obtenção de novas propriedades tem despertado grande interesse em vários campos da ciência de materiais. Em processos de separação, é de considerável interesse o uso de materiais com propriedades básicas extremamente diferentes. Entre os suportes mais usados está a sílica gel, um material com tamanho de partículas e porosidade bem definidas, elevada área superficial, e estabilidades mecânica, química e térmica elevadas. Neste contexto, a sílica gel modificada com grupos organofuncionais pode ser utilizada para a adsorção de íons metálicos em soluções aquosas e não aquosas, pré-concentração e separação de íons metálicos. Neste trabalho, a sílica gel 60 (Merck), com tamanho de partículas entre 0,2 e 0,05 mm e área superficial específica de 486 m2.g-1, foi quimicamente modificada em duas etapas. Primeiro, a sílica gel foi quimicamente modificada com 3-cloropropiltrimetoxisilano, resultando o 3-cloropropil sílica gel (CPSG). Na segunda etapa, o produto resultante, CPSG, reagiu com 2-mercaptopirimidina e 4-amino-2-mercaptopirimidina, resultando os materiais sólidos 2-mercaptopirimidina-propil sílica gel (MPSG) e 4-amino-2-mercaptopirimidinapropil sílica gel (AMSG). As quantidades de grupos funcionais conectados na superfície da sílica gel, N0, foram 7,007 x 10-4 mols e 7,416 x 10-4 mols de moléculas por grama de sílica, para MPSG e AMSG, respectivamente. Conhecendo a área superficial específica e assumindo que as moléculas cobrem uniformemente a superfície, a densidade média, d, das moléculas ancoradas e a distância intermolecular média, l, podem ser calculadas aplicando as equações d = N0 N/SBET e l = (l/d) 1/2 , onde N é o número de Avogadro. Os valores calculados são d = 1,42 moléculas.nm2 e l = 0,979 nm, e d = 1,166 moléculas.nm2 e l = 0,926 nm, para MPSG e... (Resumo completo, clicar acesso eletrônico abaixo). / Abstract: The combination of different type of materials for achieving novel properties has always been of high interest in many fields of the materials sciences. The use of materials with extremely different basic properties, like organic and inorganic compounds, is of considerable interest in separation processes. Among the supports the most used is silica gel, a material of well-established particle sizes and well-define porosity, high surface area, and high mechanical, chemical, and thermal stability. In this context, silica gel modified with organofunctional groups has been used for adsorption of metal ions from aqueous and non-aqueous solutions, pre-concentration and separation of metallic ions. In this work, silica gel 60 (Merck) having secondary particles sized between 0,2 and 0,05 mm and specific surface area of 486 m2.g-1 was modified using a two step approach. First, the silica gel was chemically modified with 3- chloropropyltrimetoxysilane, resulting the 3-chloropropyl-silica gel (CPSG). Second, the resultant product, CPSG, reacted with 2-mercaptopyrimidine and 4-amino-2- mercaptopyrimidine, resulting the solid materials 2-mercaptopyrimidine-propyl-silica gel (MPSG) and 4-amino-2-mercaptopyrimidine-propyl-silica gel (AMSG). The quantities of functional groups attached on the silica gel surface, No, were 7,007 x 10-4 mols e 7,416 x 10-4 mols .g-1 of molecules per gram of silica, for MPSG and AMSG, respectively. It being known the specific surface area and assuming that the molecules uniformly cover the surface, the average density, d, of the attached molecules and the average intermolecular distance, l, can be calculated by applying the equations: d = N0 N /SBET and l = (l/d)1/2, where N is Avogadro's number. The calculated values were d = 1,042 molecules.nm-2 and l = 0,979 nm and d = 1,166 molecules.nm-2 and... (Complete abstract click electronic address below). / Mestre

Synthetic fragrances (musk) are artificially produced organic compounds. It is used as fragrance ingredient in personal care products. Substances from this group have the ability to withstand the cleaning process in wastewater treatment plants. The physico-chemical properties of musk compounds cause their accumulation in the living and non-living components of the ecosystem, where they behave as persistent pollutants. The adsorption process is considered to be one of the most widely used separation and purification processes. The adsorption processes of a solution of sixteen synthetic fragrances took place with biochar and activated carbon. Solid phase microextraction (SPME) was used as a method for extracting analytes. Gas chromatography coupled with mass spectrometry (GC-MS) was applied for final analysis, time of flight analyzer was used as detector. The data were fitted with adsorption isotherms.

No description available.

PhD (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / High levels of pollutants in water are found to have poisonous effects on human health. Due to increasing awareness about the environment and strict environmental regulations, wastewater treatment has become a very important aspect of research. Thus, this makes the adsorption of pollutants an urgent matter. The aim of this research was to investigate the adsorption capacity of black cumin seeds in the removal of cobalt-Co(II), nickel-Ni(II), copper-(II), chromium-Cr(VI), lead-Pb(II), and methylene blue (MB) dye from aqueous solution. In this research work the black cumin seeds were reacted with sodium hydroxide (NaOH), hydrochloric acid (HCl), phosphoric acid (H3PO4), potassium permanganate (KMnO4) and sulfuric acid (H2SO4). Thereafter it was carbonized at 200 and 300 °C and functionalized with magnetite-sucrose nanoparticles and further carbonized at 600 °C to improve the adsorption capacity of the materials towards different pollutants. The seeds were characterized by scanning electron microscopy (SEM), thermogravimetric analyser (TGA), X-ray diffractometer (XRD), Brunauer, Emmett and Teller (BET) and Fourier transformed infrared (FTIR) spectroscopy. The SEM images showed that the surface morphology of the treated adsorbents was more porous and had cavities more than the starting material. The TGA profile showed a major weight loss between 198-487 °C which was due to disintegration of cellulose, lignin and hemicellulose. The XRD spectra of adsorbents showed broad peaks at 2θ value of 21° associated crystalline lignocellulose content. FTIR results showed that the adsorbents had functional groups such as hydroxyl (-OH), carboxyl (-COOH), amide (-NH) and carbonyl (-C=O). The BET surface area of pristine black cumin seeds was 2.7 m2/g and increased after treatment with KMnO4 and H3PO4 to 10.1 and 9.3 m2/g respectively. The surface area of the carbon black cumin seeds was 11.67 m2/g whilst the activation of carbon from black cumin seeds with 10 and 20% H2SO4 gave the surface area of 20.14 and 21.54 m2/g respectively. The seeds activated with 20% H2SO4 showed larger pore width of 7.13 nm compared to 6.81 and 3.78 nm after treatment with 10% H2SO4 and carbon black cumin seeds respectively. The results show that there is an increase in surface area and pore size for both 10 and 20% H2SO4 in comparison with carbon black cumin seeds. The adsorption of Co(II), Ni(II), Cu(II), Cr(VI) and Pb(II) and MB in the solution was investigated by studying the effect of initial concentration, contact time, temperature and pH. The batch adsorption experiments were conducted using different ion solution concentrations of 20, 40, 60, 80 and 100 mg/L, contact time was determined at intervals of 1, 5, 10, 15, 20, 30, 60, 90 and 120 min, while temperature was studied at 298, 303, 313, 333 and 353 K. On the other hand, the effect of pH on all solutions was studied at pH 1, 3,5,7 and 9. The results showed that the acid treated black cumin seeds (AT-BCS) and base treated black cumin seeds (BT-BCS) were successfully used for quaternary adsorption study of Cu(II), Co(II), Pb(II) and Ni(II) ions from aqueous solution. The results for the adsorbents indicated that the BT-BCS adsorbed more metals than AT-BCS and the UT-BCS. The maximum capacity for BT-BCS was 190.7 mg/g for Cu(II) whilst AT-BCS and UT-BCS showed capacities of 180.1 and 135 mg/g respectively for Pb(II). The uptake of Cr(VI) and Cd(II) ions onto pristine black seeds (PBS), KMnO4 black seeds (KMBS) and H3PO4 black seeds (H3BS) treated adsorbents showed that the trend for Cr(VI) ions was KMBS>H3BS>PBS with capacities of 16.12, 15.98 and 10.15 mg/g respectively. Meanwhile the adsorption of Cd(II) ions showed maximum capacities of 19.15, 19.09 and 16.80 mg/g for KMBS, H3BS and PBS respectively. Carbon from black cumin (CBC) seeds was modified with 10 % and 20 % sulfuric acid (H2SO4) then carbonized at 200 °C to obtain the activated adsorbents of ACBC-10 and ACBC-20. The new adsorbents were used for the adsorption of Cd(II) and methylene blue (MB). The adsorbents maximum trend for Cd(II) was ACBC-10>ACBC-20>CBC meanwhile the trend for methylene blue (MB) dye was ACBC-20>ACBC-10>CBC. The overall capacities showed that the prepared materials adsorbed more MB dye (16.42 mg/g) than Cd(II) ions (13.65 mg/g). The preparation of carbon from black cumin seeds (BCC) and activation with 10 and 20 % sulfuric acid (H2SO4) at 300 °C to obtain new adsorbents namely (BCAC-10) and (BCAC-20) respectively was used for the adsorption of Pb(II) ions and MB dye from aqueous solution. The maximum adsorption of Pb(II) ions was 17.19, 17.71 and 17.98 mg/g onto BCC, BCAC-10 and BCAC-20 respectively. Whilst for MB dye it was 11.63, 12.71 and 16.85 mg/g onto BCC, BCAC-10 and BCAC-20 respectively. The utilization of pristine Nigella Sativa (PNS) and magnetite-sucrose functionalized Nigella Sativa (FNS) seeds as the adsorbents for the uptake of Cr(VI) and Pb(II) ions from synthetic wastewater revealed that the maximum adsorption capacities for Cr(VI) were 15.6 and 13.0 mg/g onto PNS and FNS composites respectively at pH 1. On the hand, the maximum sorption capacities for Pb(II) ions were 39.7 and 37.9 mg/g onto PNS and FNS respectively at pH 5. The sorption study of Cr(VI), Cd(II) ions and MB dye by pristine Nigella Sativa (PNS) seeds, defatted and carbonized Nigella Sativa seeds from aqueous solution was investigated. The PNS seeds were treated using acetone (then named ANS) and N,N dimethylformamide (named DNS). The defatted ANS and DNS adsorbents were carbonized at 600 °C and named CANS and CDNS. The results of pristine, defatted and carbonized seeds maximum capacities were compared with each other and found that CANS had highest adsorption capacity of 99.82 mg/g for MB, 96.89 mg/g for Cd(II) and 87.44 mg/g for Cr(VI) followed by CDNS with 93.90, 73.91 and 65.38 mg/g for MB, Cd(II) and Cr(VI) respectively. ANS capacities were 58.44, 45.28 and 48.96 mg/g whilst DNS capacities were 48.19, 32.69 and 34.65 mg/g for MB, Cd and Cr(VI) respectively. PNS had the lowest sorption capacities at 43.88, 36.01 and 19.84 mg/g for MB, Cd and Cr(VI) respectively. Therefore, this makes black cumin seeds a promising material for use in wastewater treatment to mitigate metal ions and dye pollution.