A presente pesquisa teve por objetivo a investigação da influência do tamanho de partículas floculadas na eficiência da clarificação de águas para abastecimento por flotação por ar dissolvido (FAD) com o emprego de método e equipamento para a aquisição e análise de imagens especialmente desenvolvidos, tendo em vista à caracterização da distribuição de tamanho de flocos e microbolhas de ar, bem como, o estudo dos aglomerados bolhas-floco (em termos de número de microbolhas de ar aderidas e velocidade ascensional) presentes no processo de flotação e comparação dos dados experimentais àqueles obtidos em simulação com o emprego do modelo matemático proposto por Reali (1991). Os ensaios foram realizados com água sintética (turbidez de 7,5±0,2 NTU; cor aparente de 38±1 uC; alcalinidade de 29,8±0,6 mg\'CA\'CO IND.3\'/L; condutividade de 59,3±0,8 \'mü\'S/cm; UV254nm de 0,128±0,004 \'CM POT.-1\'), a qual foi coagulada com a aplicação de 1,9 mg/L de \'AL POT. 3+\' (pH de 6,6±0,05) e divididos em duas Fases: Fase 1 - ensaios preliminares realizados em escala de laboratório, com o emprego do flotateste; Fase 2 - ensaios realizados em unidade piloto de flotação. Os resultados alcançados demonstraram que: i) a distribuição de tamanho de partículas floculadas influenciou diretamente a clarificação por flotação da água em estudo, sendo que as melhores condições de floculação foram aquelas que conduziram à formação, em sua maioria, de partículas floculadas com diâmetro médio de Feret acima de 300 \'mü\'m; ii) os menores valores residuais dos parâmetros analisados na água em estudo foram alcançados com o emprego do tempo de floculação de 17 min, entretanto a FAD foi capaz de operar também com boa eficiência com a utilização de tempo de floculação de 10 min; iii) o método e equipamento desenvolvidos nesta pesquisa para a aquisição e análise de imagens demonstraram constituir importantes ferramentas para a obtenção das distribuições de tamanho de flocos e microbolhas de ar, bem como, para a determinação do número de microbolhas de ar aderidas às superfícies dos flocos e da velocidade ascensional dos aglomerados bolhas-floco gerados no processo de flotação; iv) mesmo com as diversas simplificações adotadas no desenvolvimento do modelo matemático analisado e considerando as condições experimentais utilizadas nesta pesquisa, foi possível verificar para a água em estudo e para as condições operacionais empregadas nesta pesquisa, que a modelação matemática proposta por Reali (1991) foi capaz de fornecer subsídios para uma adequada estimativa do número de microbolhas de ar aderidas aos flocos, bem como, das velocidades ascensionais dos aglomerados bolhas-floco. / The goal of this research was to investigate the flocculated particles size distribution influence on the dissolved air flotation (DAF) efficiency. Special image acquisition method and equipment were used to characterize the flocculated particles and air microbubbles size distribution, as well as, the clusters (in terms of microbubbles number adhered and rise velocity) in the contact zone outlet of the DAF unit. Besides that, the experimental results were compared with those obtained from the DAF modeling proposed by Reali (1991). The trials were carried out with synthetic water (temperature of 26.0 ± 0.5oC; turbidity of 7.5±0.2 NTU; apparent color of 38±1 CU; alkalinity of 29.8±0.6 mg\'CA\'\'CO IND.3\'/L; conductivity of 59.3±0.8 \'mü\'S/cm; UV254nm of 0.128±0.004 \'CM POT.-1\'), that it was coagulated by applying 1.9 mg/L of \'AL POT.3+\' (22.5 mg/L alum). The trials were divided into two phases: Phase 1 - preliminary tests carried out in laboratory facilities (flotatest); Phase 2 - tests carried out in pilot facilities (DAF pilot unit). The results showed that: i) the flocculation conditions interfered directly on the efficiency of DAF process, and the best flocculation conditions were those that conducted to formation of flocculated particles size with Feret mean diameter above 300 \'mü\'m; ii) the best results were obtained applying flocculation time of 17 min, however, DAF was also capable of operating with a satisfactory efficiency when applying flocculation time of 10 min; iii) the special image acquisition method and equipment developed in this research proved to be a important tool to characterize the flocculated particles and air microbubbles size distribution, as well as, the number of air microbubbles adhered to the flocs surface and the clusters rise velocity; iv) the DAF modeling developed by Reali (1991) provided a reliable prediction of the microbubbles number adhered to the flocs surface, as well as, the clusters rise velocity.

A presente pesquisa descreve o preparo, caracterização e aplicação de novos adsorventes aplicados ao tratamento de efluentes contendo corantes. Os adsorventes produzidos neste estudo foram: Carvão ativado produzido por pirólise assistida por micro-ondas (AMWCST), a partir de um lodo coletado em uma Estação de Tratamento de Efluentes de curtume; e, biomassa fúngica tratada termicamente (BTV) a partir do fungo Trametes sp SC-10, os quais foram caracterizados de acordo a suas propriedades de textura e química de superfície e foram aplicados na remoção de corantes em solução aquosa e efluentes. Nesta pesquisa também se avaliou a eficiência do processo combinado entre coagulação-floculação e adsorção usando o AMWCST. Em suas propriedades estruturais, o AMWCST apresentou uma área superficial BET de 491,0 m2 g-1 e um volume total do poro de 0,440 cm3g-1, com distribuição de tamanho de poro majoritariamente mesoporosa; entretanto o BTV apresentou baixa área superficial destacando-se a formação de mesoporos. Foram estudados os equilíbrios e cinéticas de adsorção e sua correlação com modelos empíricos, para os sistemas AMWCST/PA-210 (Preto Ácido 210), e VA-357(Vermelho Ácido 357) e BTV/ AA-161 (Azul ácido 161). Para os dois primeiros sistemas empregando carvão ativado, a isoterma de adsorção de Liu foi a que descreveu melhor os dados de adsorção com capacidades máximas de 1108 mg g-1 e 589,5 mg g-1 a 298 K para PA-210 e VA-357. Para os estudos cinéticos, o modelo de ordem fraccionário de Avrami foi o melhor modelo ajustado para os dados experimentais. A BTV no entanto, mostrou uma capacidade máxima de biossorção de AA-161 de 221,7 mg g-1 a 303 K. O modelo de Langmuir foi o modelo que melhor descreveu os dados experimentais de equilibrios de biossorção e o Modelo Fraccionário de Avrami foi o que melhor descreveu a cinética de biossorção para o corante. A eficiência de remoção do adsorvente AMWCST no efluente sintético simulado foi de 93,79% e do BTV em um efluente simulado similar ao do processo de acabamento molhado de couro foi de 89,47%, indicando que a BTV é também um bom biossorvente para o tratamento de efluentes industriais. Finalmente, enquanto ao estudo de combinação de processos de coagulação-floculação com adsorção usando o AMWCST, este mostrou resultados eficazes na remoção do corante PA-210, em efluentes do processo de acabamento molhado, obtendo 85,20% de remoção do corante em comparação com o carvão comercial, o qual apresentou 88,64%. Além disso, utilizando o AMWCST, obtiveram-se reduções de 68,44%, 13,44% e 42,81% para COT, sódio total e amônio. / The present research describes the preparation, characterization and application of new adsorbents for the treatment of effluents contaminated with dyes. An adsorbent was activated carbon produced by pyrolysis microwave-assisted (AMWCST), from a sludge collected at a tannery Treatment Plant; The other adsorbent was a thermally treated fungal biomass (BTV) from Trametes sp. SC-10 fungi, which were characterized according to their texture and surface chemistry properties and were applied in the removal of dyes in aqueous solution and effluents. In this research, the efficiency of the combined coagulation-flocculation and adsorption process using the AMWCST was also evaluated. As for the texture properties, the AMWCST presented a BET surface area of 491.0 m2g-1 and a total pore volume of 0.440 cm3g-1, with mesoporous pore size distribution; However, BTV presented low surface area, highlighting the formation of mesopores. As for adsorption equilibria and kinetics and their correlation with theoretical models, for the AMWCST / AB-210, and AR-357 and BTV/AB-161 systems. For the first two systems using activated carbon, the Liu adsorption isotherm was the model that best described the adsorption data with maximum capacities of 1108 mg g-1 and 589,5 mg g-1 at 298 K for AB- 210 and AR- 357. For the kinetic studies, the Avrami fractional order model was the best-fit model for the experimental data. BTV however, showed a maximum AB-161 biosorption capacity of 221.7 mg g-1 at 303K. The Langmuir model was the model that best described the experimental data of biosorption equilibria and the Avrami Fractional Model best described the kinetics of biosorption for the dye. The adsorption efficiency of the AMWCTS in the synthetic simulated effluent was 93.79% and the BTV in a simulated effluent similar to that of the wet-end process in the leather industry was 89.47%, indicating that BTV is also a good biosorbent for the treatment of industrial effluents. Finally, while studying the combination of coagulation-flocculation processes with adsorption using the AMWCST, it showed efficient results in the removal of the AB-210 dye in wet-end process effluents, obtaining 85.20% dye removal compared with commercial activated carbon, which had 88.64%. In addition, using AMWCST, reductions of 68.44%, 13.44% and 42.81% were obtained for TOC, total sodium and ammonium.

Este trabalho teve como propósito investigar a cinética de floculação de água bruta com baixa turbidez, utilizando o sulfato de alumínio (Al2(SO4)3o18H2O) e o cloreto férrico (FeCl3o6H2O) como coagulantes. Os resultados experimentais foram obtidos em ensaios de \"jar test\". A água bruta utilizada nos ensaios foi preparada em laboratório, simulando um manancial superficial eutrofizado contendo células da cianobactéria Microcystis aeruginosa. Foram testadas 5 dosagens distintas de cada coagulante, 3 valores de G, 2 valores de TAS e 12 tempos de floculação. Utilizou-se a turbidez como medida principal de avaliação dos resultados experimentais. O valor de turbidez inicial (N0) foi corrigido, levando-se em consideração o acréscimo de turbidez em função das dosagens de coagulante. Determinou-se que as dosagens mais efetivas, em termos de remoção de turbidez, foram 20 mg.L-1 para o sulfato de alumínio e 40 mg.L-1 para o cloreto férrico (ambas expressas como massa de coagulante). Para ambos os coagulantes, constatou-se que G = 20 s-1 e TAS = 27 m3.m-2.dia-1 resultaram nas melhores eficiências de remoção de turbidez. Verificou-se também a variação do potencial zeta em função das dosagens de coagulante. Observou-se que o aumento da dosagem de coagulante leva à redução do potencial zeta, aproximando-o do ponto isoelétrico. Porém, o ponto isoelétrico não necessariamente coincide com a melhor eficiência em termos de remoção de turbidez. Com base nos resultados experimentais, foi proposta uma modificação ao modelo clássico da cinética de floculação de suspensões coloidais. Nesta, foi incluso um segundo termo referente à ruptura de flocos (quebra irreversível). O ajuste do modelo proposto foi obtido através de procedimentos de iteração numérica computacional com a função \"Solver\" do programa Microsoft Excel®. Foram calculados os valores das constantes KA, KB e KC do modelo proposto. Amostras do lodo gerado nos ensaios de cinética de floculação foram caracterizadas visualmente através de microscopia eletrônica de varredura (MEV). / The purpose of this work was to investigate flocculation kinetics of low-turbidity raw water, using aluminum sulfate (Al2(SO4)3o18H2O) and ferric chloride (FeCl3o6H2O) as coagulants. Experimental results were obtained in jar tests. Raw water used in the jar tests was prepared in laboratory, simulating a eutrophic natural water source containing cells of the cyanobacteria Microcystis aeruginosa. 5 different coagulant doses were tested for each coagulant, 3 G values, 2 SLR values and 12 flocculation times. Turbidity was selected as the major parameter for experimental results analysis. Initial turbidity values (N0) were corrected taking into account turbidity increase due to coagulant dosing. In terms of turbidity removal, it was determined that the most effective dosage for aluminum sulfate was 20 mg.L-1, and for ferric chloride, 40 mg.L-1 (both expressed as coagulant mass). For both coagulants, it was found that G = 20 s-1 and SLR = 27 m3.m-2.day-1 resulted in the best turbidity removal efficiencies. Zeta potential variation, due to coagulant dosing, was also verified. It was noted that increasing coagulant dosing led to zeta potential reduction, bringing it closer to the isoelectric point. However, the isoelectric point does not necessary coincides with the best turbidity removal efficiency. Based on the experimental results, it was proposed a modification to the classic colloidal suspension flocculation kinetics model. In this modification, a second term regarding floc rupture (irreversible breakage) was included. Through computer numeric iteration using Microsoft Excel®\'s \"Solver\" function, the proposed model adjustment was obtained. Kinetics constants KA, KB e KC values, from the proposed model, were calculated. Sludge samples, generated during flocculation kinetics tests, were visually characterized through scanning electronic microscopy (SEM).

Orientador: Edson Pereira Tangerino / Banca: Dib Gebara / Banca: Carlos Gomes da Nave Mendes / Resumo: Novas tecnologias para o tratamento de água vêem sendo desenvolvidas e suas combinações podem apresentar bons resultados principalmente quando submetidas a variações sazonais de origem natural e antropicas. A crescente poluição dos corpos d'água causa florescimentos de algas e cianobactérias nos mananciais, com aparecimento de sabor e odor na água bruta, podendo ocorrer também a liberação de toxinas pelas cianobactérias. Os processos de tratamento de água convencionais têm apresentado deficiências quanto à remoção de cianobactérias e cianotoxinas, principalmente quanto ao aspecto de remoção das células viáveis e na capacidade de remover as toxinas extracelulares. As cianobactérias retidas no lodo dos decantadores representam riscos à qualidade final da água tratada. O presente projeto de pesquisa consistiu em experiência com floco-decantador de manta de lodo acoplado a flotador por ar dissolvido, formando um conjunto composto pelos dois tipos de equipamentos ou tecnologias e ainda com dispositivo limitador de manta. O objetivo da pesquisa foi avaliar o desempenho da instalação proposta quando submetida a variações da qualidade da água bruta, principalmente quando submetido à sobrecarga de algas e cianobactérias, simulando possíveis florações nos mananciais. Os resultados dos ensaios no modulo experimental com água natural apresentaram remoção satisfatória de turbidez , com valores abaixo de 3,0 uT da água floco-floto-decantada e em torno de 0,1 uT da água filtrada. Os ensaios realizados com água natural com presença elevada de algas e cianobactérias, evidenciaram a importância da unidade de flotação, com remoção de clorofila_a de 82% na água decantada/flotada e próximo de 99% na água filtrada, em relação à água bruta, sendo que a turbidez manteve-se abaixo de 3 uT na saída do modulo floco-floto-decantador e a turbidez... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: New technologies for water treatment have been developed and their combinations can produce good results especially when subjected to seasonal variations of natural and anthropogenic. The increasing pollution of water bodies causes blooms of algae and cyanobacteria in water sources, with the appearance of taste and odor in raw water, but may also occur the release of toxins by cyanobacteria. The processes of conventional water treatment have shown deficiencies in the removal of cyanobacteria and cyanotoxins, especially on the aspect of removal of viable cells and the ability to remove extracellular toxins. Cyanobacteria retained in the sludge of the sedimentation tanks pose to the final quality of treated water. This research project was to experiment with floc-settling sludge blanket coupled to dissolved air flotation, forming a group composed of two types of equipment or technology, and with relief device blanket. The research aimed to evaluate the performance of the proposed development when subjected to variations in raw water quality, especially when subjected to the overload of algae and cyanobacteria to simulate possible blooms in the springs. The results of tests on an experimental module with natural water showed satisfactory removal of turbidity, with values below 3 uT decanted and around 0,1 uT filtered water. Tests conducted with water with high presence of algae and cyanobacteria, have highlighted the importance of unity flotation Chlorophyll "a" with removal of 82% in the decanted water / rappel and around 99% in filtered water compared to raw water, and the turbidity remained below 3 uT the output of modulo-flake-floto sedimentation and turbidity of filtered water was below 0,6 uT. The limiting device of the ground and periodic removal of sludge, decreased the retention time of the cells retained in the sludge which may have prevented the release of toxins into the water... (Complete abstract click electronic access below) / Mestre

As microalgas são fontes sustentáveis de bioprodutos com alto valor agregado, que podem ser utilizados para diversos fins, tais como alimento, matéria-prima e energia. Devido a isso, as microalgas se condicionam como uma solução para suprir o aumento da população mundial, com a vantagem de serem obtidas sem uso de energia fóssil e terras agricultáveis. Entretanto, os custos associados à produção de microalgas ainda é muito alto, o que inviabiliza o seu uso em grande escala. A combinação do tratamento de esgoto e o crescimento de microalgas é uma promissora alternativa para reduzir os custos relacionados ao cultivo. No entanto, o esgoto afluente das ETEs brasileiras são altamente diluídos, o que torna o seu uso impraticável do ponto de vista técnico e econômico para o cultivo de microalgas. Nesse contexto, o presente trabalho propõe uma mistura de esgoto (esgoto sanitário e de suinocultura), visando aumentar a concentração de nutrientes (carbono, nitrogênio e fósforo), para o cultivo de Chlorella sorokiniana. Os resultados são promissores, com produção média de 1 g.L-1 de C. sorokiniana e remoção média de carbono inorgânico dissolvido (CID), ortofosfato (PO43-) e amônia (NH3) de 46 a 56%, 40 a 60% e 100%, respectivamente. Foi verificado que a remoção de NH3 por air stripping durante o cultivo afetou negativamente a produtividade de biomassa e remoção de nutrientes. Além disso, algumas propostas de separação foram estudadas, uma vez que essa etapa pode representar de 20 a 60% dos custos totais de produção de microalga. A alteração de pH seguida pela FAD apresentou altas eficiências (96,5 a 97,9%) nos pH de 12 a 13. A coagulação seguida pela FAD foi estudada utilizando coagulantes orgânicos e inorgânicos. As melhores doses foram de 10 mg·L-1 Zetag 8185; 75 mg·L-1 Tanfloc SG; 500 mg·L-1 Al2(SO4)3 e 1000 mg·L-1 FeCl3 que apresentaram uma eficiência máxima de 98,4; 94,5; 95,4; 96,7%; respectivamente. A sedimentação pela floculação alcalina com precipitados de fosfato de cálcio é eficiente, porém pode ser sensível à presença de compostos proteicos presentes no esgoto (albumina e matéria orgânica bacteriana). Entretanto, foram encontradas condições (pH 8 e 10) e concentrações (10 mg·L-1), nas quais a floculação alcalina foi efetiva. / Microalgae are sustainable sources of high-value bioproducts that can be used for a variety of purposes, such as food, raw materials and energy. For this reason, the microalgae are conditioned as a solution to supply the increase of the world population, with the advantage of being obtained without using fossil energy and arable land. However, the costs associated with the production of microalgae are still very high, which makes it impossible to use them in large-scale. The combination of wastewater treatment and microalgae cultivation is a viable option to reduce expenses related to cultivation. However, municipal wastewater from the centralized Brazilian sanitation system is highly diluted, and it is technically and economically impractical to use it for microalgae cultivation. In this context, the present work proposes a wastewater mixture (municipal and swine wastewater), aiming to increase the concentration of nutrients (carbon, nitrogen and phosphorus) for the cultivation of Chlorella sorokiniana. The results are promising, C. sorokiniana production reached around 1 g.L-1, with dissolved inorganic carbon (DIC), ortophosphate (PO43-) and ammonia (NH3) average removal from 46 to 56%, 40 to 60% and 100%, respectively. It was found that NH3 removal by air stripping during cultivation negatively affected the biomass productivity and nutrient removal. In addition, some harvesting method proposals have been studied, since this step represents 20 to 60% of the total costs of microalgae production. The pH modulation followed by DAF showed high efficiencies (96.5 to 97.9%) at pH 12 to 13. Coagulation followed by DAF was studied using organic and inorganic coagulants. The best doses were 10 mg·L-1 Zetag 8185; 75 mg·L-1 Tanfloc SG; 500 mg·L-1 Al2(SO4)3 and 1000 mg·L-1 FeCl3 which had a maximum efficiency of 98.4, 94.5, 95.4, 96.7%, respectively. Alkaline flocculation using calcium phosphate precipitates is an efficient harvesting method, but it can be sensitive to the presence of protein compounds in the wastewater (albumin and bacterial organic matter). However, it was found conditions (pH 8 e 10) and concentrations (10 mg·L-1) at which alkaline flocculation was effective.

Kirka Boron Plant in Eski

Saccharomyces cerevisiae is an excellent experimental model organism to study various biological processes owing to its versatile genetics, biochemistry, and standard laboratory conditions. S. cerevisiae shows distinct biological responses under nutritional starvation conditions. S. cerevisiae undergoes dimorphic transition from a unicellular yeast form to a multicellular pseudohyphae (Gimeno et al., 1992) under nitrogen starvation, but in the complete absence of a fermentable carbon source, it undergoes gametogenesis called sporulation (Mitchell, 1994). While the signal transduction cascades and regulatory controls under nutritional starvation conditions are studied to great extent, the role of S. cerevisiae core RNA polymerase II (pol II) is not much understood. S. cerevisiae core RNA pol II consists of 12 subunits (Woychik and Hampsey, 2002), which is organized into a ten-subunit core and the Rpb4/7 subcomplex (Edwards et al., 1991). Rpb4/7 subcomplex is known to play important roles in stress survival (Choder 2004; Sampath and Sadhale, 2005.). S. cerevisiae rpb4 null diploid strains show reduced sporulation levels but exhibits a predisposition to pseudohyphal morphology (Pillai et al., 2003). Overexpression of Rpb7 partially rescues some of these defects (Sharma et al., 1999; Sheffer et al., 2001). Rpb7 is a highly conserved protein but Rpb4 is the least conserved amongst all RNA pol II subunits at the sequence level. Rpb4 and Rpb7 also affect different cellular functions, which are not directly dependent on each other. (a) Relative levels of RNA pol II subunits Rpb4 and Rpb7 differentially affect starvation response in Saccharomyces cerevisiae S. cerevisiae rpb4 null diploid strains show reduced sporulation levels as compared to wild type but exhibits pseudohyphal predisposition. Overexpression of RPB7 partially rescues the sporulation defect but results in an exaggeration of the pseudohyphae phenotype. We generated S. cerevisiae strains expressing different levels of Rpb4 and Rpb7 proteins in the same strains and analyzed their effect on sporulation and pseudohyphal morphology. We observed that sporulation is dependent on Rpb4 because sporulation level gradually increases with an increase in the Rpb4 protein level in the strain. Rpb7 reduces sporulation level but enhances pseudohyphal exaggeration in a dose-dependent manner. Rpb4 is dominant over Rpb7 in both the starvation responses because strain expressing an equimolar ratio of Rpb4 and Rpb7 protein exhibits RPB4+ phenotypes. (b) Domainal organization of Saccharomyces cerevisiae Rpb7 orthologs reflects functional conservation Rpb7 orthologs are known in eukaryotes and archaebacteria. The primary structure of Rpb7 is conserved. We chose Rpb7 orthologs from Candida albicans, Schizosaccharomyces pombe and Homo sapiens sapiens to investigate whether Rpb7 orthologs are also functionally conserved. We observed that all the orthologs tested are functionally conserved because they can complement the absence of RPB7 in S. cerevisiae. However, we uncovered functional differences amongst Rpb7 orthologs with respect to its function in rpb4 null strain and ess1 ts strain. Furthermore, we made N and C-terminal chimeric RPB7 constructs from these orthologs with S. cerevisiae Rpb7. These chimeras also can replace ScRpb7 in S. cerevisiae. However, functional differences were observed with each chimera pair in rpb4 null strain and ess1 ts strain, showing that the N and C-terminal domains of Rpb7 protein can be genetically dissected. The genetic observation on the domainal organization of Rpb7 orthologs is strengthened by the crystal structure of Rpb7 (Armache et al., 2005), which shows that Rpb7 is structurally organized into an N terminal RNP domain and a C terminal OB fold domain. (c) The Rpb7 subunit of Candida albicans RNA polymerase II induces lectin-mediated flocculation in Saccharomyces cerevisiae The Rpb7 ortholog of C. albicans is a conserved functional ortholog of ScRpb7. We observed that CaRpb7 induces Ca2+-dependent flocculation and agar-invasive growth in S. cerevisiae. CaRpb7 overexpression induces very high transcript levels of FLO1 and FLO11. We believe that the observed flocculation and agar-invasive phenotypes are due to Flo1 and Flo11 respectively, because Flo1 and Flo11 contribute mainly to cell-cell adhesion while Flo11 contributes mainly to cell-substrate adhesion (Verstrepen and Klis, 2006; Lo et al., 1998; Guo et al., 2000). Pathway analysis revealed that CaRpb7-induced flocculation is dependent on Mss11 transcriptional activator. Two-hybrid analysis revealed that CaRpb7 does not physically interact with transcriptional repressors known to repress FLO gene transcription, however genetic analysis revealed that CaRpb7 is epistatic to the repressor Sfl1. Rpb7 orthologs possess conserved domains with potential RNA binding ability (Orlicky et al., 1999) and ScRpb7 is known to play in mRNA stability (Lotan et al., 2007). The possibility of CaRpb7 specifically affecting the stability of FLO gene transcripts is being pursued.

Biological degradable polymers on a basis of renewable raw materials, such as polysaccharides, represent promising alternatives to synthetic polymers used as flocculant or stabilizing agents. Polysaccharides derived from potato starch and chitosan have been modified with benzyl- and the first one with additionally cationic hydroxypropyl-trimethylammonium groups of different degrees of substitution (DS). The aim of this work was to characterize the solution properties of these novel amphiphilic polysaccharides concerning the impact of their DS on charge density, particle size, dynamic surface tension and viscosity behaviour. The work is further focused on investigations on flocculation properties of these amphiphilic polyelectrolytes in dispersions of kaolin and silica to identify the interplay between charge density and hydrophobicity. Flocculation efficiency has been evaluated via joint analysis of charge density measurements (using polyelectrolyte titration), turbidity and TOC measurements, as well as dynamic surface tension measurements applying the drop profile analysis. Particle sizes and particle size distributions have been determined by dynamic light scattering and laser diffraction methods. In addition, these amphiphilic starch derivatives have been used to remove substances which impact negatively the paper production process when using recycled paper, so called stickies. Model suspensions have been studied using a multitude of different measurement techniques with the aim to predict a “sticky potential” and to reduce containing dissolved and colloidal substances such as micro stickies. The surface activity and viscometric behaviour have been studied of solely cationic and moderately and highly substituted, amphiphilic polysaccharides in salt-free and 0.05 M NaCl aqueous solution. For the first time dynamic surface tension measurement results have been correlated with particle sizes and apparent charge density. Rheological investigation of large concentration ranges (0.01–20 g/L) was used to discuss Huggins plots and typical polyelectrolyte behaviour for all polysaccharide derivatives could be found. Overlap concentration and, in dilute aqueous solution, intrinsic viscosity could be determined. For polysaccharide solution in dilute regime semi-empirical equations of Rao and Wolf have been applied, making it possible to get insights to polyelectrolyte conformation in dependence on the DS of both substituents. It is shown that for intrinsic viscosity a change of the impact of both substituents takes place when having derivatives with enhanced hydrophobicity. Data evaluation via the ratio of both DS values had been successfully utilized and thus, the applied method has been identified as being a promising tool to compare a multitude of starch derivatives with substituents of different polarity in various degrees of substitution to get tendencies regarding overall hydrophobicity. Moderate hydrophobic substitution was found to lead to a decrease of the efficient flocculant dose and to an increase of the flocculation window width. Amphiphilic starch derivatives with high DS of hydrophobic moieties showing strong hydrophobic association are effective only at significantly higher doses, but in a broader concentration range compared to cationic starch of the same DS. Joint analysis of adsorption isotherms and flocculation test data has revealed, that the surface coverage required to induce phase separation ranges between 10 and 25 % and is minimal for amphiphilic starch derivatives. This gave the evidence of the complex mechanism of flocculation via combination of electrostatic “charge patch” interactions and bridging. Concerning sticky reduction experiments by systematically studying the interactions between the novel amphiphilic starch derivatives and the model suspension it turned out, that dynamic surface tension is a very suitable property to characterize the surface active compounds in the model suspension giving additional information about the sticky potential of waste water, e.g. white water, being a new and sensitive method to describe the parameter “hydrophobicity”. Moderate cationic and hydrophobic starch derivatives have been proved to be the most effective ones for sticky removal.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A coagulação, um processo importante no tratamento convencional de efluentes, promove a retirada de partículas leves demais para sedimentarem por ação da gravidade (coloides). A sedimentação destas partículas torna-se possível com a adição de agentes coagulantes, geralmente sais metálicos. Entretanto, o grande inconveniente no uso destes sais são os resíduos metálicos que permanecem no lodo, e que podem contaminar o solo. Agentes coagulantes à base de polieletrólitos orgânicos têm se mostrado interessantes pela sua capacidade de retirar matéria orgânica de efluentes. Este trabalho objetivou testar a eficiência de dois polieletrólitos naturais, quitosana e Tanfloc®, como coagulantes, para redução de DQO, turbidez e cor aparente de efluente advindo de um abatedouro e frigorífico de suínos, e de compará-la com a eficiência do cloreto férrico. A sequência de ensaios, conduzidos em Jar Test, foi realizada segundo planejamento experimental pré-definido para cada um dos coagulantes, com planejamento fracionado seguido de DCCR. A quitosana promoveu aumento considerável da DQO, ao invés de sua redução, mostrando-se ineficaz na redução desta resposta. Entretanto, como auxiliar de coagulação a quitosana favoreceu a formação de flocos maiores. O Tanfloc® proporcionou formação de flocos grandes em pH básico (7,75) e flocos pequenos em pH ácido (5,25). Em condição ótima e em pH básico, ainda para o Tanfloc®, a redução máxima foi de 86% para turbidez e 34% para cor aparente. Em pH ácido, a melhor redução foi de 96% para turbidez e 78% para cor aparente. A redução conseguida para DQO foi de cerca de 50%, independentemente do pH aplicado. Estes resultados foram satisfatórios e condizentes com o esperado para o coagulante Tanfloc®. Quanto ao cloreto férrico, este apresentou, de forma geral, um desempenho inferior ao Tanfloc®. Os resultados mostram que o Tanfloc® foi eficaz no papel de coagulante primário, substituindo, com vantagens, o cloreto férrico no tratamento de coagulação, floculação e sedimentação do efluente de estudo. / Coagulation, an important process in the conventional treatment of effluents, promotes the removal of particles too light to sediment by gravity action (colloids). The settling of these particles becomes possible with the addition of coagulating agents, generally metal salts. However, the major drawback in the use of such salts are metallic residues remaining in the sludge, which can contaminate soil. Coagulant agents based on organic polyelectrolytes have been interesting for their ability to remove organic matter from effluents. This study aimed to test the efficiency of two natural polyelectrolytes, chitosan and Tanfloc®, As coagulants, for the reduction of COD, turbidity and apparent colour of effluent coming from a pig slaughterhouse, and to compare it with the efficiency of ferric chloride. The sequence of tests, conducted in Jar Test, was performed according to a predefined experimental design for each of the coagulants, with fractional planning followed by DCCR. Chitosan promoted a considerable increase in COD, rather than its reduction, proving ineffective in reducing this response. However, as a coagulation aid, chitosan favored the formation of larger flakes. Tanfloc® provided formation of large flakes at basic pH (7.75) and small flakes at acid pH (5.25). In optimum condition and at basic pH, a maximum reduction of 86% for turbidity and 34% for apparent colour was obtained. At acid pH, the reduction achieved for the responses was 96% for turbidity and 78% for apparent colour. The COD reduction was about 50% regardless of the pH. These results were satisfactory and consistent with that expected for the coagulant. Regarding ferric chloride, it generally presented a lower performance than Tanfloc®. The results showed that Tanfloc® performed very well the role of primary coagulant, favorably replacing ferric chloride in the treatment of coagulation, flocculation and sedimentation of the study effluent.

L'objectif de la thèse est d'étudier l'évolution de la morphologie de flocs soumis à des conditions hydrodynamiques turbulentes. A cet effet, des expériences de floculation par neutralisation de charge en présence de sels sont mises en œuvre, dans deux géométries de réacteurs, sous différentes conditions hydrodynamiques. Dans un premier temps, des expériences de floculation sont réalisées sous conditions hydrodynamiques fixées. D'une part, un suivi en ligne de la floculation de microsphères de latex en jar test est effectué par granulométrie à diffraction laser. Plus le taux de cisaillement moyen G caractéristique de l'hydrodynamique globale du réacteur est élevé, plus la cinétique de floculation est rapide ; la distribution de diamètres équivalents demeure alors monomodale et présente une autosimilarité. L'évolution de la dimension fractale Df représentative de l'ensemble de la population montre une compaction des agrégats au cours du temps, d'autant plus marquée que G est élevé. D'autre part, la caractérisation de nombreuses propriétés morphologiques de flocs de bentonite formés dans un réacteur de Taylor-Couette est effectuée par analyse d'images (méthode in situ non intrusive). Un grand nombre d'images sont acquises, permettant de déterminer avec précision l'évolution temporelle des distributions des propriétés morphologiques ainsi que de leurs moments. Bien que les caractéristiques de taille et de forme soient liées, leur dépendance à l'hydrodynamique n'est pas la même. Des flocs produits dans des conditions hydrodynamiques différentes, et dont les distributions de tailles sont similaires, présentent des formes différentes. Le rayon de giration des flocs est corrélé à la micro-échelle de Kolmogorov tandis que leur circularité semble corrélée à la vitesse de rotation du cylindre interne. Dans un second temps, un séquençage des conditions hydrodynamiques consistant en deux cycles de rupture-refloculation est effectué après une première étape de floculation dans le réacteur de Taylor-Couette. L'irréversibilité après rupture est montrée. La refloculation produit des flocs de tailles plus réduites et de formes plus régulières et l'état stationnaire est atteint plus rapidement, sans phase de restructuration significative, contrairement à ce qui est observé après la première étape de croissance. Si la contrainte appliquée lors de la rupture est suffisamment élevée, le second cycle a peu d'influence sur la population de flocs. En revanche si la contrainte de rupture est moins importante, chacun des deux cycles forme des flocs plus compacts et plus lisses, mais aussi plus petits. L'étape de rupture produit des floculi qui deviennent alors les briques élémentaires pour l'étape de refloculation suivante. La taille des flocs obtenus lors de ces étapes de refloculation est limitée par l'hydrodynamique, mais leur structure est déterminée par la taille et la structure des floculi. Enfin, la problématique de la modélisation de la floculation par Bilan de Population (BP) est abordée. Une équation de BP tenant compte de la dimension fractale est formulée pour modéliser les expériences de floculation de latex en jar test. Les seuls paramètres variables du modèle sont les valeurs expérimentales de G et Df. Basée sur la méthode de la quadrature des moments (QMOM), la résolution du BP permet de décrire convenablement l'évolution des six premiers moments de la distribution de tailles expérimentale et de certains diamètres caractéristiques, aux différentes conditions hydrodynamiques mises en œuvre. / The objective of this work is to study the time evolution of floc morphology under turbulent hydrodynamic conditions. For this purpose, flocculation by charge neutralization in the presence of salts is realized within two reactor geometries under various hydrodynamic conditions. As a first step, flocculation experiments under constant hydrodynamic conditions were realized. On the one hand, a laser light scattering technique is used for an on-line monitoring of latex microsphere flocculation conducted in a jar. The higher the global shear gradient G, the faster the flocculation kinetics, and thus the equivalent diameter distribution tends to keep monomodal and autosimilar. The time evolution of the fractal dimension Df, representative for the whole population, shows that aggregates get more compact with time, and this trend is more pronounced when G is higher. . On the other hand, bentonite flocculation is realized in a Taylor-Couette reactor. Various morphological properties are measured by an in situ non-intrusive method of image acquisition and analysis. Each measurement consists of a large number of images, allowing the precise calculation of property distributions and their moments over time. Although size and shape are obviously correlated, their dependency to hydrodynamics is different. Flocs of similar sizes produced under different hydrodynamic conditions exhibit different shapes. The sizes are calibrated by the turbulence as the double radius of gyration is close to Kolmogorov microscale, whereas the circularity seems correlated to the rotation speed. As a second step, a hydrodynamic sequencing is imposed in the Taylor-Couette reactor, in order to realize two breakup and reflocculation cycles after a first flocculation phase. The irreversibility is shown. Reflocculation after breakup produces smaller sizes, more regular shapes, and the steady state is reached faster since there is no restructuration phase such as the one observed after the initial growth step. When the breakup shear is high enough, the second cycle has very little impact. However, if the breakup shear is lower, each of the two cycles produces more compact and smoother, but also smaller flocs. The breakup step produces flocculi that are the building blocks for the next re-flocculation step. The, floc size is conditioned by hydrodynamics, whereas floc structure is determined by flocculi size and structure. Finally, the issue of modelling is addressed. A population balance (PB) equation accounting for the fractal dimension is formulated, in order to model the latex flocculation experiments. The only varying model parameters are the experimental values of G and Df. The PB, solved using the quadrature method of moments, allows to adequately describe the temporal evolution of the first six moments of the experimental distribution obtained under three hydrodynamic conditions.