La dégradation des ressources en eaux par la présence de matières organiques (MO) et de micropolluants nécessite la mise en œuvre de procédés de production d’eau potable robustes. Dans ce contexte, de nombreuses municipalités françaises comme Saint Cloud et Angers ont décidé d’implanter un procédé d’adsorption sur charbon actif en poudre couplé à l’ultrafiltration (CAP/UF). Le CAP est utilisé en amont des membranes afin d’éliminer les traces de micropolluants tandis que les membranes d’UF assurent une qualité d’eau produite excellente et constante au cours du temps. Cependant, les retours d’expérience montrent une dégradation des performances de séparation liée notamment à un vieillissement des matériaux membranaires ainsi qu’une vulnérabilité du procédé vis-à-vis de certains micropolluants émergents tels que les composés organiques polaires (PMOCs). Les travaux réalisés au cours de cette thèse visent à mieux comprendre les conséquences du vieillissement chimique des membranes utilisées dans ces procédés et d’évaluer l’efficacité d’élimination de micropolluants afin de proposer des voies d’optimisation. Plus particulièrement il a été montré que la cause principale de vieillissement est l’exposition au chlore des membranes durant les phases de lavage modifiant les propriétés des matériaux. En effet, les nombreux outils de caractérisation utilisés ont permis de mettre en évidence une corrélation entre la dégradation de l’agent hydrophile des membranes et l'augmentation de la perméabilité lors de l'exposition au chlore. L’étude des performances membranaires a mis en évidence une altération de la résistance au colmatage vis-à-vis de la MO pour les membranes exposées au chlore. Cependant les résultats obtenus pour évaluer les performances de sélectivité des membranes vis-à-vis de virus n’ont pas souligné d’altérations majeures. Les essais d’adsorption ont démontré l’efficacité limitée du CAP pour la rétention des PMOCs. En effet, parmi les molécules testées, les molécules aromatiques les plus hydrophobes sont efficacement adsorbées par le CAP tandis que les plus polaires sont peu éliminées. Finalement, l’utilisation de la nanofiltration ou l’osmose basse pression, présentant des taux de rétention en moyenne supérieurs à 90%, en font des solutions techniques de choix pour l’élimination des PMOCs. / The degradation of water resources by the presence of organic matter (OM) and micropollutants requires the implementation of robust drinking water production processes. In this context, many French municipalities such as Saint Cloud and Angers have decided to set up a powdered activated carbon adsorption process coupled to ultrafiltration (PAC/UF). PAC is used upstream of membranes to remove traces of micropollutants while UF membranes provide excellent and constant water quality over time. However, the feedback reveals a degradation of the separation performances related in particular to an aging of the membrane materials and a vulnerability of the process towards some emerging micropollutants such as polar organic compounds (PMOCs).The work carried out during this thesis aims to better understand the consequences of the chemical aging of the membranes used in these processes and to evaluate the micropollutants removal efficiency in order to propose optimization ways. More particularly it has been shown that the main cause of aging is the chlorine exposure of the membranes during washing phases modifying the properties of the materials. In fact, the numerous characterization tools used have made it possible to demonstrate a correlation between the degradation of the hydrophilic agent of the membranes and the increase in the permeability during exposure to chlorine. The study of the membrane performances revealed an alteration of the resistance to fouling towards OM for membranes exposed to chlorine. However, the results obtained to evaluate the selectivity performance of the membranes with respect to viruses have not underlined any major alterations. Adsorption tests have demonstrated the limited efficiency of PAC for PMOCs removal. Indeed, among the molecules tested, the most hydrophobic and aromatic molecules are effectively adsorbed on PAC while the more polar ones are slightly adsorbed. Finally, the use of nanofiltration or low-pressure reverse osmosis, with average rejection rates over 90%, makes them the technological solutions of choice for the removal of PMOCs.

Bei der Aufbereitung von Rohwässern zu Trinkwasser fallen in der Regel unvermeidbare Rückstände an, die den gesetzlichen Bestimmungen entsprechend entsorgt werden müssen. Schlammhaltige Wässer, die den größten Anteil an Wasserwerksrückständen einnehmen, entstehen bei der Spülung von Filtern und enthalten nahezu alle aus dem Rohwasser entfernten Stoffe und nicht im Trinkwasser verbleibende Aufbereitungschemikalien. Während früher in vielen Wasserwerken Teile des schlammhaltigen Filterspülwassers nach einem Sedimentationsvorgang wieder in den Aufbereitungsprozess zurückgeführt wurden, ist dies in Deutschland auf Grund einer möglichen Beeinträchtigung der Trinkwasserqualität bei mikrobiologisch belasteten Wässern (z. B. Oberflächenwasser) ohne eine adäquate Behandlung (z. B. Ultrafiltration) nicht mehr erlaubt. Somit müssen schlammhaltige Filterspülwässer anderweitig entsorgt werden, z. B. durch eine Einleitung in die Kanalisation. Die dabei auftretenden Auswirkungen auf Abwasserbehandlungsanlagen sind noch nicht ausreichend bekannt. In der vorliegenden Arbeit werden unterschiedliche Ultrafiltrationsmodule (Kapillarmembranmodul und getauchtes Modul) hinsichtlich ihrer Eignung zur Aufbereitung aluminiumhaltiger schlammhaltiger Filterspülwässer und damit zur Rückführung des entstehenden Filtrates in den Aufbereitungsprozess untersucht. Die grundsätzliche Eignung beider Modulsysteme wird nachgewiesen. Bei Verwendung von getauchten Modulen kann auf eine vorangehende Sedimentationsanlage verzichtet werden. Als kritisch muss unabhängig vom gewählten Modulkonzept die Entsorgung des anfallenden Retentates angesehen werden, da die gesetzlich vorgeschriebenen Grenzwerte der Indirekteinleitung für mehrere Parameter nicht eingehalten werden. Bilanzierungen der relevanten Schadstoffe ergeben, dass der Schadstoffeintrag überwiegend diffus mit dem Rohwasser in das Wasserwerk erfolgt. Zur Untersuchung von Auswirkungen der Einleitung aluminiumhaltiger schlammhaltiger Filterspülwässer aus der Oberflächenwasseraufbereitung auf die Abwasserbehandlung wurden labortechnische Versuche zur Ermittlung des Phosphatadsorptionspotenzials durchgeführt. Neben der Abhängigkeit der Phosphatadsorptionskapazität vom pH-Wert wurde der Einfluss der Feststoffkonzentration des schlammhaltigen Filterspülwassers in Versuchen mit Modellwasser nachgewiesen. Eine Erhöhung der Feststoffkonzentration wirkt einer möglichst hohen Ausnutzung des Adsorptionspotenzials entgegen. Während für die Ultrafiltrationsbehandlung gegenüber der Indirekteinleitung ein Kostenvorteil ermittelt wird, ist die für die Nutzung des Phosphatadsorptionsanteils verfügbare Schlammmenge für einen alleinigen Einsatz in der Kläranlage bei gleichen Einzugsgebieten nicht ausreichend. / In most water treatment plants (WTPs), during the water purification process, residuals are generated that have to be disposed according to current regulations. Most of the residuals are derived from filter backwash processes (i. e. spent filter backwash water, SFBW) and contain substances that are removed from the raw water. In addition, in the spent filter backwash water, chemicals can be found that are required for the operation of the water treatment process and do not remain in the drinking water. Over recent decades, SFBW has been returned to the beginning of the water treatment plant (WTP) after a sedimentation process in order to reduce the amount of water being discharged. Concerns over the recycling of microorganisms, of heavy metals or precursors for disinfection by-products, have led to a significant reduction of the number of WTPs that directly return filter backwash water to the water treatment process. According to German technical standards, the reuse of SFBW might only be possible after the application of groundwater infiltration or an equivalent technique. Because of an almost complete recovery of particles and microorganisms, ultrafiltration treatment is a proven alternative to groundwater recharge of SFBW. In this work, different ultrafiltration modules for the treatment and reuse of SFBW are compared. Capillary as well as submerged membrane modules are suitable for the treatment of SFBW. If submerged membrane modules are used, no sedimentation period prior to ultrafiltration treatment is necessary. As a consequence of the accumulation of particulate matter including heavy metals and other compounds in the retentate during ultrafiltration treatment, threshold values of several regulations cannot be met, and either the discharge of retentate into the sewer will be charged or alternative disposal options must be considered. Mass balances for an entire WTP showed most of these contaminants to originate from non-point sources in the watershed. Lab-scale experiments are performed for the examination of the phosphate adsorption potential of SFBW derived from surface water treatment using aluminum-based coagulants. Besides a strong influence of the pH-value present in the SFBW, an influence of the TSS-concentration of SFBW on phosphate adsorption capacity could be demonstrated. Elevated TSS-concentrations resulted in a lower phosphate adsorption capacity of the investigated SFBW. While ultrafiltration treatment with subsequent reuse of SFBW might be cheaper than the discharge to the sewer system, the amount of SFBW required for a complete phosphate removal in the wastewater treatment plant is to large and therefore, no economic advantage of phosphate adsorption could be demonstrated

Thesis (MSc)--Stellenbosch University, 2001. / ENGLISH ABSTRACT: At the Mondi Kraft paper mill in Piet Retief, paper machine effluent is pre-treated by means of dissolved air flotation (DAF) and a mierostrainer prior to ultrafiltration (UF). Despite the rigorous pre-treatment of the effluent, severe fouling of the UF membranes still persisted, resulting in a sharp decrease in operational flux. In an attempt to improve the flux performance of the UF membranes an investigation was launched into the possible causes of membrane fouling. The study yielded the following results: Ultraviolet-visible (UV-Vis) spectrophotometric analyses of varIOUS effluent samples collected from different locations at the mill indicated the presence of aromatic compounds. Lignosulphonate appeared to be the main constituent in all the samples analysed. UV-Vis spectrophotometry was also performed on fouling extracted from membranes In order to evaluate the different approaches attempted to reduce membrane fouling. Most of the UV-Vis spectra obtained did not show the absorbance maxima below 210 nm that were seen for the paper machine effluent, DAF product, lignosulphonate and mierostrainer product. This indicated that the compounds with absorbance at lower wavelengths did not foul the membranes to the same extent as the aromatic substances with absorbance maxima between 230 and 400 nm. The influence of pH on the absorption of the various effluent samples was also investigated. An increase in pH resulted in (1) a "shift" in the wavelength scans from a lower to a higher wavelength, suggesting ionisation (deprotonation) with a subsequent delocalization of electrons and (2) an increase in the turbidity. The increase in turbidity which accompanied the Increase in pH could be explained by complex formation between the carboxylate ions, phenolic groups and divalent metal ions present in the effluent. Inductively coupled plasma analyses of several effluent samples with pH values 7 and 13 indicated the presence of significant amounts of Ca2+ ions in the effluent. There was a significant decrease in the Ca2+ levels with an increase in pH, which supported the hypothesis that Ca2+ might contribute to complex formation. This resulted in a decrease in solubility and an increase in turbidity. The addition of a chelating agent (ethylenediaminetetra-acetic acid disodium salt) to an effluent solution at pH 13 redissolved the precipitate and considerably reduced the turbidity. The subsequent addition of CaCh again induced precipitation and increased turbidity, confirming the role of Ca2+ in complex formation. Gel permeation chromatographic analyses of mierostrainer product at pH 13 showed the formation of high molecular mass organo-calcium complexes. The exact molecular mass of the complexes present in the mierostrainer product could not be determined by electro spray mass spectrometry because of their poor ionisation ability. Atomic force microscopy and scanning electron microscopy (SEM) showed distinct differences in the membrane surface texture before and after fouling. Furthermore, SEM images of the UF membranes exposed the limited ability of the 30 urn microstrainer, installed downstream from the DAF unit, to remove residual fibres from the DAF product. Static fouling experiments performed on all the flocculants and coagulants used In the paper-making process at the mill showed that none of these substances fouled the UF membranes. Cleaning of the UF membranes with Triton XIOO®, a nOn-IOnIC surfactant, caused a temporary increase in the operating flux to values higher than that of the initial flux. Mechanical cleaning of the UF membrane surface with spongebalIs proved to be one of the most effective and successful methods to prevent flux loss caused by fouling. Pre-coating of the UF membranes with Plutonic" FI08, another non-ionic surfactant, did not promote membrane productivity. Evaluation of various types of membranes indicated that hydrophilic or negatively charged membranes withstood membrane fouling more effectively than hydrophobic UF membranes under the same operating conditions. / AFRIKAANSE OPSOMMING: By Mondi Kraft se papier meule in Piet Retief word afloopwater vanaf die papiermasjiene vir hergebruik met behulp van ultrafiltrasie (UF) behandel. Opgeloste lugflotasie (OLF) en mikrosiwwing word as voorbehandeling vir die UF membraanproses ingespan. Ondanks die intensiewe voorafbehandeling wat toegepas word, vind daar geweldige aanvuiling van die UF membrane plaas wat tot die vinnige verlaging in bedryfsfluks aanleiding gee. 'n Ondersoek na die moontlike oorsake van membraan-aanvuiling het die volgende bevindinge opgelewer: Ultraviolet-sigbare (UV-Vis) spektroskopie van water monsters wat by die meule versamel is, het die teenwoordigheid van aromatiese komponente aangetoon, met lignosulfonaat die hoofkomponent in al die monsters wat ontleed is. Ekstrakte afkomstig van aangevuilde membrane is ook met behulp van UV-Vis-spektroskopie geanaliseer om verskeie benaderings te evalueer om 'n afname in membraan-aanvuiling te bewerkstellig. Die oorgrootte meerderheid spektra het nie die absorpsie maksima onder 210 nm aangetoon wat teenwoordig was in monsters van die papier masjien afloopwater, OLF uitvloeisel, lignosulfonaat en mikrosif produkwater nie. Dit het aangedui dat die komponente wat by laer golflengte absorbeer nie die UF membrane in dieselfde mate aanvuil as daardie komponente wat by hoër golflengtes (tussen 230 en 400 nm) absorbeer nie. Die invloed wat pH op die absorpsie van komponente teenwoordig in die onderskeie afloopwatermonsters het, is ook ondersoek. 'n Toename in pH het bygedra tot (1) 'n verskuiwing in die spektra vanaf 'n lae na 'n hoër golflengte vanweë ionisasie (deprotonering) met gevolglike delokalisasie van elektrone en (2) 'n toename in turbiditeit. Die toename in turbiditeit wat verband hou met die toename in pH was verduidelik aan die hand van kompleksvorming tussen die karboksilaat ione, fenoliese groepe en divalente metaal ione in die afloopwater. Induktief gekoppelde plasma analise van verskeie water monsters by pH 7 en 13 het die teenwoordigheid van 'n groot hoeveelheid Ca2+ aangetoon. 'n Verlaging in die vlakke van opgeloste Ca2+ het met die toename in pH verband gehou. Dit het die moontlike verbintenis tussen Ca2+ en kompleksvorming ondersteun wat bygedra het tot die afname in oplosbaarheid en toename in turbiditeit. Die byvoeging van etileendiamientetra-asynsuur-dinatriumsout, 'n kelerings reagens by afloopwater (pH 13) het die presipitaat weer in oplossing gebring en die turbiditeit merkwaardig verlaag. Die byvoeging van CaCh het weer presipitasie geïnduseer, met 'n gevolglike toename in turbiditeit. Hiermee is Ca2+ se rol in kompleksvorming bevestig. Gelpermeasie-chromatografiese analise van die mikrosif produk (pH 13) het die vorming van hoë molekulêre massa organo-kalsium komplekse bevestig. Dit was egter nie moontlik om met behulp van massaspektrometrie die korrekte molekulêre massa van die komplekse te bepaal nie vanweë hul onvermoë om te ioniseer. Atomiese krag mikroskopie en skandeer elektron mikroskopie (SEM) het duidelik die voor en na verskil getoon wat aanvuiling op die membraantekstuur gehad het. 'n SEM foto van die aangevuilde UF membraan het die onvermoë van die mikrosif blootgelê om oorblywende vesels vanuit die OLF produkwater te verwyder. Resultate bekom gedurende passiewe aanvuilingseksperimente het aangetoon dat al die in-proses flokkulante en koagulante wat gebruik word by die papier meule geen bydrae tot die aanvuiling van die UF membrane maak nie. Skoonmaak van die UF membrane met Triton XIOO® bring 'n verhoging in bedryfsvloed teweeg, maar die verhoging, wat hoër as die oorspronklike vloed is, is kortstondig. Meganiese skoonmaak van die buismembrane met behulp van sponsballe blyk die mees effektiewe skoonmaakmetode te wees. Voorafbehandeling van die UF membrane met Plutonic" F 108 het nie die membraanproduktiwiteit verhoog nie. Daar is ook bevind dat hidrofiliese of negatief gelaaide membrane groter weerstand bied teen aanvuiling in vergelyking met hidrofobiese UF membrane onder dieselfde bedryfstoestande.

Linfomas são cânceres que se iniciam a partir da transformação maligna de um linfócito no sistema linfático. Os linfomas são divididos em duas categorias principais: os linfomas de Hodgkin e todos os outros linfomas, denominados linfomas não-Hodgkin (LNH). Os pacientes com LNH são comumente tratados com radioterapia apenas ou combinada com quimioterapia utilizando-se de anticorpo monoclonal anti-CD20, principalmente o rituximab (MabThera&reg). O uso de anticorpos monoclonais (Acm) conjugados à quelantes bifuncionais radiomarcados com radionuclídeos metálicos ou lantanídeos é uma realidade de tratamento para portadores de LNH pelo princípio de radioimunoterapia (RIT). Este estudo concentrou-se nas condições de conjugação do anticorpo monoclonal rituximab (MabThera&reg) com grupamentos quelantes bifuncionais DOTA e DTPA. Na marcação dos Acm conjugados com lutécio-177, foram estudadas as condições de pré-purificação do Acm, condições de conjugação, determinação de número de quelantes acoplados à molécula do anticorpo, purificação do anticorpo conjugado, radiomarcação do anticorpo conjugado, com lutécio-177, purificação do anticorpo marcado, a ligação específica in vitro dos compostos marcados às células Raji, e distribuição biológica em camundongos BALB/c sadios. As três metodologias empregadas na pré-purificação do anticorpo (diálise, cromatografia de exclusão molecular com coluna Sephadex G-50 e ultrafiltração) demonstram-se eficientes e proporcionaram recuperação da amostra superior a 90%. A metodologia de ultrafiltração foi considerada a mais simples e prática, podendo ser aplicada a procedimentos rotineiros de produção de radiofármacos. Além disso, proporcionou a recuperação final de amostra de 97% em microlitros. Nas conjugações do anticorpo com os quelantes DOTA e DTPA em razões molares diferentes do Acm:quelante, observou-se número de grupamentos quelantes acoplados à molécula do Acm proporcional à razão molar estudada. Quando foi avaliada a influência de condições diferentes de conjugação no número de quelantes acoplados à molécula do Acm, não foram observadas diferenças significativas, com resultados de pureza radioquímica (PR) inferior a 80% em todas as condições estudadas. Na comparação de métodos de purificação do Acm conjugado, a abordagem inédita apresentada neste estudo, na qual a cromatografia de exclusão molecular foi combinada com a ultrafiltração resultou em maior eficiência na purificação e preservação da estrutura do anticorpo. Nos estudos de radiomarcação do anticorpo conjugado com DOTA e DTPA, os imunoconjugados de DTPA apresentaram, de forma geral, maior eficiência de marcação com resultados reprodutíveis quando comparados com os imunoconjugados de DOTA, considerando-se as diferentes razões molares utilizadas. As metodologias cromatográficas empregadas no controle de pureza radioquímica do composto radiomarcado proporcionaram a discriminação das diferentes espécies radioquímicas no meio de marcação. A metodologia de purificação do composto conjugado e radiomarcado utilizada proporcionou a obtenção de compostos com alta pureza radioquímica, 97,4&plusmn;1,3% (DOTA 1:50) e 98,7&plusmn;0,2% (DTPA 1:50). Nos estudos de ligação específica às células tumorais Raji, o anticorpo conjugado com quelante DTPA nas razões molares de 1:50 e 1:20 apresentaram perfil semelhante de ligação, com aumento da porcentagem de ligação específica proporcional à concentração celular, enquanto que o imunoconjugado na razão molar de 1:10 apresentou alta porcentagem de ligação não específica. Os resultados obtidos nos estudos de biodistribuição in vivo do anticorpo conjugado e radiomarcado nem sempre se mostraram compatíveis com a biodistribuição de anticorpos radiomarcados íntegros. No caso do quelante DOTA, o imunoconjugado obtido a partir da razão molar 1:20, apresentou melhores características de biodistribuição. No caso do quelante DTPA, a razão molar utilizada pareceu refletir diretamente no clareamento sanguíneo do anticorpo e todas as razões molares utilizadas apresentaram instabilidade in vivo. / Lymphomas are malignancies or cancers that start from the malign transformation of a lymphocyte in the lymphatic system. Lymphomas are divided in two major categories: Hodgkin lymphoma and non-Hodgkin lymphoma (NHL). Patient with NHL are generally treated with radiotherapy alone or combined with immunotherapy using monoclonal antibody rituximab (MabThera&reg). Currently, monoclonal antibodies (Mab) conjugated with bifunctional chelate agents and radiolabeled with metallic or lanthanides radionuclides are a treatment reality for patients with NHL by the principle of radioimmunotherapy (RIT). This study focused on the conditions of conjugation of Acm rituximab (MabThera&reg) with bifunctional chelating agents DOTA and DTPA and labeling with 177-luthetium. Various parameters were studied: method of Acm purification, conditions of Acm conjugation and the determination of the number of chelate coupled to the Acm, the purification of the conjugated Mab, labeling conditions with lutetium-177, purification of the radiolabeled immunoconjugate, radiochemical purity (RP), in vitro specific binding determination to Raji cells (Human Burkitt) and biological distribution performed in normal BALB/c mouse. The three methodologies employed in pre-purification of Acm (dialysis, size exclusion chromatograph and ultrafiltration) demonstrated to be efficient; they provided sample recovery exceeding 90%. However, the methodology of ultrafiltration resulted in greater sample recovery and in microliters. The number of chelate attached to the Mab molecule was proportional to the molar ratio studied. When the influence of different conditions of conjugation in the number of chelate bounded to the Mab was studied, no notable differences were observed. The RP < 80% was observed in all the methods applied. Purification of the conjugated antibody by different methods showed that the innovative combination of Sephadex and ultrafiltration methods resulted in higher efficiency of purification. The optimized conditions for purification of the conjugated antibody preserved the protein integrity. Radiolabelling studies of DOTA and DTPA immunoconjugated showed that DTPA derivatives presented, in general, radiochemical yield superior than DOTA conjugated Mab, considering the different molar ratios studied. The chromatographic methods employed in the RP determination were efficient to separate the different radiochemical species presented in the reaction medium. The methodology used in the purification of the labeled Mab resulted in labeled compounds with high radiochemical purity, 97.4&plusmn;1.3% (DOTA 1:50) and 98.7&plusmn;0.2% (DTPA 1:50). Considering specific cell binding assays (Raji cells), the Mab conjugated to DTPA at 1:50 and 1:20 molar ratios presented similar results, and the percent of cell binding were proportional to the cell concentration, whereas the cell binding for 1:10 molar ratio showed high percent of nonspecific cell binding. The results of in vivo biodistribution studies of labeled Mab not always were compatible with the biodistribution of intact radiolabelled antibody. The DOTA immunoconjugated produced at 1:20 molar ratio, showed better performance in biodistribution studies. In the case of DTPA immunoconjugated, the blood clearance seems to be influenced by the molar ratio applied and the immunoconjugated produced with DTPA chelate at different molar ratio resulted in high in vivo instability compounds.

Submitted by Eunice Novais (enovais@uepg.br) on 2018-07-31T12:05:01Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tatiane Bovaroti.pdf: 1677408 bytes, checksum: 74791391260b47b48abc127d7af4af68 (MD5) / Made available in DSpace on 2018-07-31T12:05:01Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tatiane Bovaroti.pdf: 1677408 bytes, checksum: 74791391260b47b48abc127d7af4af68 (MD5) Previous issue date: 2018-04-12 / Preocupados com a intrusão de água do mar, escassez e má qualidade das reservas de água doce no mundo, diversos países têm estudado e proposto sistemas de alta tecnologia que sejam viáveis para a dessalinização de água salobra ou salina. Este trabalho teve como objetivo principal avaliar a eficiência de um sistema de ultrafiltração (UF) como pré-tratamento, seguido de abrandamento e osmose reversa (OR) para a dessalinização de água salobra em escala piloto, instalado no balneário de Praia de Leste, litoral do estado do Paraná. Para a obtenção da água salobra foi realizada a mistura da água do rio das Pombas com a água do mar até a concentração de 1500 (± 100) mg. L-1 de sólidos dissolvidos totais (SDT). O sistema foi projetado para a produção de 1 m3.h-1 de água doce (permeado da OR) e operou por aproximadamente 3h por dia durante vinte dias não consecutivos. Analisaram-se amostras de nove pontos de coleta durante a primeira (A), segunda (B) e terceira (C) hora de operação. Para a avaliação da qualidade da água os parâmetros analisados foram: SDT, condutividade elétrica, pH, temperatura, cor aparente, turbidez, alcalinidade total, dureza total, cálcio, cloreto, sulfato, coliformes totais e E.coli. Para avaliação da eficiência do sistema, calculou-se a taxa de recuperação e o fluxo de filtração, bem como a leitura de outros parâmetros operacionais como a pressão osmótica. O sistema de UF apresentou remoção média de 95,1% de turbidez e de 98,6% de cor aparente na água salobra. Constatou-se ausência de coliformes totais e E.coli no permeado. Houve variação quanto à remoção de dureza total e cálcio pelo abrandador devido ao tempo de regeneração do sistema. O sistema de OR obteve remoção média de 99,4% de SDT e a maior taxa de recuperação global (UF e OR) foi de 57,4%. / Concerned about the intrusion of sea water, scarcity and poor quality of freshwater reserves in the world, several countries have studied and proposed high technology systems that are feasible for the desalination of brackish or saline water. The main objective of this work was to evaluate the efficiency of an ultrafiltration (UF) system as a pretreatment, followed by slowing and reverse osmosis (RO) for pilot scale saline water desalination, installed in Praia de Leste – coast of the state of Paraná. To obtain the brackish water, the water of the Pombas River was mixed with sea water up to the concentration of 1500 (± 100) mg. L-1 total dissolved solids (TDS). The system was designed to produce 1 m3.h-1 of freshwater (permeate from the RO) and was operated by approximately 3 hours per day during twenty non-consecutive days. Samples from nine collection points were analyzed during the first (A), second (B) and third (C) hours of operation. In order to evaluate the water quality, the parameters evaluated were: TDS, electric conductivity, pH, temperature, apparent color, turbidity, total alkalinity, total hardness, calcium, chloride, sulfate, total coliforms and E.coli. To evaluate the efficiency of the system, the recovery rate and the filtration flow were calculated, as well as the reading of other operational parameters such as osmotic pressure. It was found absence of total coliforms and E. coli in the permeate. There was variation regarding to the removal of total hardness and calcium by the softener due to the regeneration time of the system. The RO system obtained an average of 99.4% of the TDS removal and the highest overall (UF and RO) recovery rate was 57.4%.

Milhões de toneladas de resíduos são gerados pela agroindústria todos os anos, gerando problemas ambientais e econômicos; muitos destes resíduos, entretanto, são ricos em nutrientes e compostos funcionais, o que poderia tornálos subprodutos com valor agregado. A utilização de subprodutos possibilita enriquecimento dos alimentos processados, redução de descarte no meio ambiente e melhor aproveitamento dos recursos naturais. Os talos de beterraba são um exemplo de resíduo com potencial a ser explorado e, assim como os bulbos, são ricos em betalaína, composto responsável pela sua coloração vermelho-violeta. Esses pigmentos são aplicáveis na indústria alimentícia como corantes naturais, mas a sua estabilidade é um dos maiores desafios frente a sua utilização. Neste contexto, este trabalho tem como objetivo principal estudar a extração, a clarificação e a estabilização de betalaínas provenientes de talos de beterraba vermelha. Para tanto, foi inicialmente estudado a viabilidade da utilização dos talos de beterraba como fonte de betalaínas e, em sequência, a extração destes compostos via esmagamento. A utilização de diferentes processamentos com vistas à melhora da extração e o seu impacto na estabilidade das betalaínas presente no extrato foram investigados: o processamento por alta pressão (HPP do inglês High Pressure Processing) e o tratamento térmico com alta temperatura por curto tempo (HTST do inglês High Temperature Short Time). Por fim, foi realizado um estudo de clarificação do extrato por meio de processo de separação por membranas (PSM). A clarificação foi aplicada por microfiltração (MF) seguido por ultrafiltração (UF). Além disto, a MF também foi operada no modo diafiltração (DF). A redução da atividade da enzima peroxidase, as características físico-químicas, a cor e a taxa de degradação das betalaínas ao longo do armazenamento foram avaliados nos extratos antes e após a clarificação. Os resultados mostraram que os extratos obtidos via esmagamento possuíam em média 45% da quantidade de pigmentos presentes no extrato dos bulbos de beterraba. O processamento por HPP não foi considerado uma boa alternativa para melhorar a extração e também não contribuiu para o aumento na estabilidade dos pigmentos presentes nos extratos. O tratamento térmico HTST causou uma pequena degradação das betalaínas; porém, quando aplicado por 120 s a 85,7 °C nos extratos com alta concentração inicial, promoveu uma redução na taxa de degradação das betalaínas da amostra tratada de 1,2 para 0,4 mg de betanina/100 ml de extrato por dia após uma semana de armazenamento. No estudo de clarificação por PSM, os experimentos de MF e UF apresentaram reduções no fluxo do permeado ao longo do processo, além de elevada tendência ao fouling, em ambas as membranas. A aplicação da MF batelada seguida por UF ocasionou uma redução de 99,5% da atividade de peroxidase. Quando a MF foi operada em modo DF, a alimentação do processo foi modificada de duas bateladas de 2 L cada para uma batelada de 3 L, aproveitando melhor os pigmentos da alimentação. Além disto, a clarificação contribuiu para a estabilidade das betalaínas, uma vez que a taxa de degradação reduziu de 0,32 e 0,41 mg de betanina/100 ml de extrato por dia para 0,2 mg de betanina/100 ml de extrato por dia no 10° dia de armazenamento. Os processos de MF, em modo batelada e DF, seguidos por UF promoveram redução na turbidez e no teor de sólidos solúveis, além de extratos clarificados com cor mais intensa, luminosa e avermelhada. / Every year a huge amount of waste is generated by agricultural industry, becoming a serious environmental and economic problem; many of these wastes, however, contain nutrients and functional compounds, which could make them by-products with added value. The use of by-products allows the enrichment of processed foods and the reduction of discard in the environment, ensuring a better use of natural resources. The beet stalks are an example of waste with potential to be explored and, as the root, are rich in betalains, whose provide their red-violet color. These pigments are applicable in the food industry as natural dyes. The stability of these pigments, however, is one of the biggest challenges of using it. In this context, this work aims to study the extraction and clarification of betalains from red beet stalks. Initially it was studied the feasibility of using beet stalks like a betalain source and, after that, the extraction of these compounds through crushing was carried out. The utilization of different processing to improve the extraction and the impact on the betalain stability present in the extract were studied: the high pressure processing (HPP) and the thermal treatment high temperature short time (HTST). Lastly, a study of clarification of the extract using the membrane separation processes (PSM) was carried out. Clarification was first applied by microfiltration (MF) followed by ultrafiltration (UF). In addition, MF was also operated in diafiltration mode (DF). The peroxidase activity reduction, physico-chemical characteristics, color and degradation rate of betalains over the storage were evaluated in the extracts before and after the clarification. The results show that the stalks extract by crushing had about 45% of the pigments content in the extract from root of beet. HPP was not considered a suitable alternative to improve the extraction and did not contribute to the increase in the stability of the pigments present in the extracts. The thermal treatment HTST caused a small degradation of betalains. However, when it was applied for 120 s at 85.7 °C, in the extracts with high initial concentration, it promoted a reduction in the betalain degradation rate of the treated sample from 1.2 to 0.4 mg of betanin/100 ml of extract per day after one week of storage. In the PSM clarification study, the MF and UF experiments, showed permeated flux reduction, indicating high fouling tendency on both MF and UF membranes. The application of MF followed by UF caused a reduction of 99.5% in peroxidase activity. When MF was operated in DF mode, the process feed was modified from two batches of 2 L each to a 3 L batch, making better use of feed pigments. In addition, the clarification experiments contributed to the betalain stability, as the betalain degradation rate reduced from 0.32 and 41 mg of betanin/100 ml of extract per day to 0.2 mg of betanin/100 ml of extract per day on the 10th day of storage. The MF processes, batch and DF mode, followed by UF promoted a reduction in the turbidity and soluble solids content and the clarified extracts had color more intense, bright and reddish.

Thesis (Master of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2017. / For more than a decade, poultry product consumption increased in developed and developing countries, with more than 470 new slaughterhouses being constructed in South Africa (SA). Customer demand for poultry products resulted in a rapidly growing poultry industry, with consequential increases in the quantity of organic solid and liquid waste being produced from the poultry slaughterhouses. Annually, the productivity and profitability within the livestock production sector has increased, an evaluation based on the number of slaughtered and sold animals. Potable water is required for these animals, resulting in the generation of high strength wastewaters. Instantaneous disposal of such wastewaters into the environment is concerning as it results in odour and the spreading of diseases in local rivers and freshwater sources. The generated poultry slaughterhouse wastewater (PSW) contains a high quantity of biodegradable organic, suspended and colloidal matter in the form of proteins, fats, oil and grease (FOG), protein from meat, blood, skin, and feathers, resulting in high Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD), which can contribute to environmental deterioration if not treated adequately before discharge. On average, PSW contains a high concentration of BOD, COD, nitrogen, pathogenic and non-pathogenic viruses, bacteria and parasites, including their eggs. These characteristics make PSW highly polluted with a large quantity of bird carcass debris including FOG. Due to the high concentration of organic matter and suspended solids in the wastewater, it is necessary to pre-treat the PSW prior to sequential anaerobic treatment. Most of the contaminants present in the PSW can be reduced by means of numerous treatment steps, i.e. physical, chemical and biological treatment. For this study, biological treatment methods, physical separation methods, and a membrane bioreactor system, were used to treat PSW. The biological treatment methods used were an anaerobic digester (AD) followed by a single stage nitrification/denitrification reactor and then a third stage in which an ultrafiltration (UF) and Microfiltration (MF) membrane bioreactor (MBR) was used. The AD used was an Expanded Granular sludge Bed Reactor (EGSB) as anaerobic digestion is one of the most effective biological wastewater treatment methods used, as it reduces the organic matter to even produce biogas as a renewable energy source. The basis of anaerobic treatment method relies on suitable bacteria cultivated in the absence of dissolved oxygen, facilitating decomposition of organic matter into a renewable source such as biogas. Similarly, biological nitrification/denitrification processes for the removal of total nitrogen (TN) in wastewater has become one of the most commonly used processes within the wastewater treatment sector. Nitrification and denitrification processes can be performed by some microorganisms within the wastewater in Wastewater Treatment Plants (WWTPs) The PSW used was collected at different times from a local poultry slaughterhouse in the Western Cape (South Africa) and stored in a refrigerator at 4°C until it was fed to the first stage of the treatment which was the EGSB. Before being fed to the EGSB, the PSW was filtered with a sieve to remove feathers and agglomerated FOG to avoid clogging of the tubing. The EGSB was inoculated with 0.747 L anaerobic granular sludge, had a working volume of 2.7 L, an inner diameter of 0.065 m and a height of 0.872 m respectively. Ceramic marbles with an average diameter of 0.0157m were placed at the bottom of the bioreactor as packing for the underdrain and to maintain the granular sludge within the heated section of the bioreactor. The EGSB was fed with three types of PSW: 50% (v/v), 70% (v/v), which was diluted with distilled water. Thereafter once the system stabilised the reactor was fed with undiluted PSW (100%). Each dilution was operated at different Hydraulic Retention Times (HRTs) and Organic Loading Rates (OLRs), with average HRTs used being 62.5, 57.5 and 49.65 h. Furthermore, the average OLRs were 1, 2 and 3 g tCOD/L.day respectively. The performance of the EGSB was determined using tCOD, Total Suspended Solids (TSS) and FOG, with overall averaged removal rates for these constituents being 69%, 98% and 92% respectively. The highest tCOD removal of 93 % (optimal efficiency) was obtained at an average HRT of 57.5 h with a corresponding average OLR of 2 g tCOD/L.day.

Reverse osmosis (RO) and ultrafiltration (UF) retentates were ultra-high temperature (UHT) processed and compared for storage life at room temperature. Viscosity studies indicated that UHT-treated, RO retentate delayed age gelation longer than UF retentate at the same total solids level (26% TS). When compared at 6.4% protein level (2x RO vs 2.7x UF where x=ratio of the feed volume to concentrate volume), the storage life for both RO and UF retentates was about 6 to 8 months. Sodium hexametaphosphate (SHMP) and disodium phosphate (DSP) at 1, 3, 5, 10, and 20 mM concentrations were incorporated prior to UHT processing of each sample to improve the shelf life. SHMP at 1 and 3 mM concentrations was effective in delaying age gelation, whereas all levels of DSP accelerated gelation. However, SHMP accelerated age gelation at concentrations of 10 and 20 mM. SHMP at 1 mM in RO retentate was more effective in delaying age gelation than the same SHMP level in two UF samples (22 and 26% TS). Analysis showed that RO/UHT-treated samples had higher soluble calcium and ionic calcium than did UF/UHT-treated samples. The coefficient of determination (R2) was .80 between soluble calcium-to-protein ratio and shelf life.

Abstract not available

Ce mémoire décrit des essais de la micro et l'ultrafiltration dynamique effectués avec trois pilotes de laboratoire, un pilote MSD à disque membranaire rotatif sur deux arbres, un pilote à disque rotatif avec une membrane organique fixe, et un pilote à cylindre tournant avec une membrane concentrique. Le module MSD a été testé en microfiltration de suspensions de CaCO3 où nous avons comparé des membranes céramiques et organiques. Les essais ont confirmé l'importance du recouvrement des disques. Ensuite, nous avons appliqué le système de MSD aux traitements des effluents modèles de surfactants anioniques (solutions de SDBS et SDS), avec une comparaison au système à disque rotatif, qui permettait une pression plus élevée de fonctionnement. En terme de flux de perméat et de taux de rétention, ces deux systèmes possèdent des avantages par rapport aux systèmes de filtration tangentielle classique. Puis, les modules à disque rotatif et à cylindre tournant ont été employés à l'ultrafiltration des solutions d'albumine bovine (BSA) pour simuler l'hémofiltration (traitement de l'insuffisance rénale aiguë).