Submitted by Lara Oliveira (lara@ufersa.edu.br) on 2017-02-01T20:26:32Z No. of bitstreams: 1 AndréMO_TESE.pdf: 5450289 bytes, checksum: 5882a0a67b8d1b236c9a9b7e9ec60dfb (MD5) / Approved for entry into archive by Vanessa Christiane (referencia@ufersa.edu.br) on 2017-03-21T14:53:28Z (GMT) No. of bitstreams: 1 AndréMO_TESE.pdf: 5450289 bytes, checksum: 5882a0a67b8d1b236c9a9b7e9ec60dfb (MD5) / Approved for entry into archive by Vanessa Christiane (referencia@ufersa.edu.br) on 2017-03-21T15:07:13Z (GMT) No. of bitstreams: 1 AndréMO_TESE.pdf: 5450289 bytes, checksum: 5882a0a67b8d1b236c9a9b7e9ec60dfb (MD5) / Made available in DSpace on 2017-03-21T15:07:20Z (GMT). No. of bitstreams: 1 AndréMO_TESE.pdf: 5450289 bytes, checksum: 5882a0a67b8d1b236c9a9b7e9ec60dfb (MD5) Previous issue date: 2016-07-15 / In spite of the fact that crystalline basement predominates with brackish water wells in Brazilian thirstland, desalination technology by reverse osmosis enables its potabilization. Since the late nineties, reverse osmosis desalination devices have been deployed in order to meet the water demand for human consumption, especially in the rural Northeast. Nevertheless, difficulties are present in such deployment like lack of operation and proper maintenance, causing stoppage thereof and producing high-level reject brine, which is usually discharged to the ground without any criteria, and its main consequence has been soil salinity increase over time. Thus, this works aims at evaluating the outcome of the reverse osmosis desalination discharge and its influence in physicochemical attributes of distinct receiver soils in rural communities from Potiguar west. This research was conducted between 2013 and 2014. At first, the communities which were supplied by catchment and treatment of desalinated water centers were registered through a cadastral survey. In order to do so, four data collection expeditions took place in different periods, raining season and drought, on the soils receiving reject brine. Three distances were used (0, 1 and 2 meters from the discharge points) with two layers for each point (0-20cm and 20-40 cm) as well as the evaluation of a) the reverse osmosis treated water quality, b) the well, c) the reject brine. Physicochemical attributes of water for irrigation was also analyzed as well as soil samples for a fertility evaluation. Data were subjected to statistical average tests by Scott Knott to verify the behavior within the points and layers according to each period and between all four periods. The waters were classified according to its use for irrigation; leakage risks and toxicity in plants. The soils were classified according to salinity, Ph considering CE and PST. In the monitored rural communities, the reversed osmosis water treatment stations produce desalinated water with low concentrations of salts, with 68% of all samples are in C1S1 rating class; 25% in C2S1 and class; only 7% in C3S1 class. Regarding the reject brine, 93% of waste water samples were classified as C3 or C4 during the four collecting periods, that is, at high or extremely high salinization risk. The different types of receiver soils of reject brine coming from such communities show meaningful alteration of their attributes and of their qualities throughout the periods, being that more noticeable during the drought periods and on the layers of soils with greater amount of clay, promoting different ratings for the same soil, being such ratings influenced directly by the waste water from desalination process / Ainda que, no Semiárido brasileiro, predomine o embasamento cristalino, com poços de água salobra, a tecnologia da dessalinização permite a sua potabilização. Desde o final da década de 1990, vem sendo implantados equipamentos de dessalinização por osmose reversa visando o atendimento da demanda hídrica para consumo humano, especialmente na zona rural do Nordeste. No entanto, dificuldades estão presentes na implantação dos equipamentos, tais como a falta de operação e manutenções adequadas que causam a paralisação dos mesmos, e a produção de rejeitos com elevados teores de sais, normalmente despejados ao solo sem qualquer critério, cujo maior impacto tem sido o aumento da salinidade do solo ao longo do tempo. Desta forma, o objetivo deste trabalho foi avaliar o rejeito gerado pela osmose reversa e sua influência nas alterações dos atributos físico-químicos de distintos solos receptores em comunidades rurais do Oeste Potiguar. A pesquisa ocorreu no período de 2013 e 2014, inicialmente, foram identificadas as comunidades abastecidas com as unidades de captação e tratamento de água por dessalinização, por meios de um levantamento cadastral. Para isto, foram realizadas 4 campanhas de coletas em diferentes períodos de seca e chuva nos solos receptores do rejeito salino, usando três distâncias (0; 1 e 2 metros do ponto de despejo), com duas camadas para cada ponto (0-20 e 20-40 cm), bem como avaliação da qualidade das águas tratadas por osmose reversa, poço e rejeito salino, dentro de cada período. Foram analisados atributos físico-químicos das águas para fins de irrigação e as amostras de solo para avaliação da fertilidade. Os dados foram submetidos a testes estatísticos de médias, por Scott Knott, verificando o comportamento dentro dos pontos e camadas de cada período e entre os 4 períodos. As águas foram classificadas quanto ao uso na irrigação; aos riscos de infiltração e toxicidade em plantas. Os solos foram classificados de acordo com a salinidade, considerando pH, CEes e PST. As estações de tratamento de água por osmose reversa nas comunidades rurais monitoradas produzem uma água dessalinizada com concentrações baixas de sais, com 68% do total das amostras estão na classe de classificação C1S1; 25% na classe C2S1 e; apenas 7% na classe C3S1. Com relação ao rejeito gerado, 93% das amostras de água de rejeito se classificaram como C3 ou C4 nos quatro períodos de coleta, ou seja, águas de alto ou extremamente alto risco de salinização. As diferentes classes de solos receptores do rejeito salino das comunidades apresentaram alterações significativas dos seus atributos e sua qualidade ao longo dos períodos, sendo mais evidente nos períodos secos e camadas de solos com maior presença de argila, promovendo classificações distintas para um mesmo solo, influenciadas diretamente pela água de rejeito do processo de dessalinização / 2017-02-01

O tratamento de efluentes industriais tem sido objeto de estudos no sentido da busca de soluções que minimizem impactos ambientais e promovam a conservação do bem natural que é a água. Nesta linha de pensamento, o presente trabalho propôs-se avaliar a viabilidade de recuperação de efluentes industriais contaminados com pesticidas do tipo piretróides em específico: a deltametrina e beta-ciflutrina. A justificativa na escolha deste tipo de componente está fundamentada na alta demanda alimentícia por parte da população mundial e o consequente acréscimo no uso dos agrotóxicos a fim de garantir a eficiência e o elevado volume de produção de alimentos. O objetivo deste trabalho foi estudar a remoção da deltametrina e da beta-ciflutrina de efluentes sintéticos aquosos por meio dos processos de osmose inversa e nanofiltração, com a utilização de membranas de poliamida. O presente estudo se justifica pelo atendimento aos padrões ambientais de concentração de piretróides no meio ambiente e reafirma o uso do sistema com membranas no tratamento de efluentes e remoção destes contaminantes. Para caracterização das membranas, foi realizado o teste de permeabilidade hidráulica, constatando diferentes linearidades de fluxo entre os dois processos, com a variação de pressão de trabalho. O desempenho dos processos foi verificado pela variação de parâmetros de meio reacional, variando a concentração dos piretróides em solução, analisando os princípios ativos isolados e também em mistura de ambos piretróides. Primeiramente se estudou a remoção da deltametrina e da beta-ciflutrina isoladamente em solução, nas concentrações de 5, 25, 50 e 100 mg L-1, sob a pressão de 5 bar. Posteriormente, avaliou-se o desempenho das membranas na remoção dos piretróides em mistura nas soluções sintéticas, com ambos os princípios ativos na concentração de 50 mg L-1, na pressão de 5 bar. Foi estudada a remoção da deltametrina e da beta-ciflutrina nos dois processos: osmose inversa e nanofiltração. Os resultados foram tratados estatisticamente por análise de variância (ANOVA) e pela análise por comparação de amostras independentes a fim de verificar a significância dos valores obtidos e a influência da variação dos parâmetros analisados. Para a faixa de concentração estudada (5, 25, 50 e 100 mg L-1) os valores encontrados de concentração de permeado foram todos consideravelmente baixos. O maior valor encontrado foi de 0,026 mg L-1 no ensaio de nanofiltração com concentração inicial de 5 mg L-1 de beta-ciflutrina em água. Os resultados apresentaram excelentes rejeições em todos os testes, seja com princípio ativo isolado ou em mistura, com rejeições maiores que 99,5% para ambos os piretróides nas concentrações testadas, sob a pressão de 5 bar. O processo de nanofiltração apresentou maiores e melhores fluxos de permeado do que a osmose inversa. Contudo, no que diz respeito à eficácia da separação, ambos processos indicaram ótimo desempenho na remoção dos piretróides, viabilizando assim, a escolha destes métodos para tratamento de efluentes contaminados com este pesticida / Treatment of industrial effluents has been the subject of numerous studies aimed at finding solutions that minimize environmental impacts and promote the recovery and / or reuse of the natural benefit which is the water. With this in mind, this study aims to evaluate the feasibility of recovery of industrial effluents contaminated with pyrethroid pesticide - in particular: the beta-cyfluthrin and deltamethrin. The justification for choosing this type of component is based on the high demand for food for the world population and consequent increase in the use of pesticides to ensure efficiency and high volume food production. The aim of this work was to study the removal of deltamethrin and beta-cyfluthrin from synthetic effluents through process of reverse osmosis and nanofiltration, with the use of polyamide membranes. This study is justified by attendance to environmental standards for pyrethroids concentration in the environment and it reaffirms the use of membranes system in wastewater treatment and in the removal of contaminants. For membranes characterization an hydraulic permeability test was performed, noting different flow linearities between the two processes, under variation of pressure. The process performance was verified by variation of parameters of reaction environment, by varying the concentration of pyrethroids in solution, examining the active ingredients alone and in mixture of both pyrethroids. First of all, we have studied the removal of deltamethrin and beta-cyfluthrin alone in solution, on concentrations of 5, 25, 50 and 100 mg L-1, under the pressure of 5 bar. Subsequently, we assessed the performance of the membranes in the removal of pyrethroid in mixture in the synthetic solutions, with both active ingredients at a concentration of 50 mg L-1, at a pressure of 5 bar. We studied the removal of deltamethrin and beta-cyfluthrin in two processes: reverse osmosis and nanofiltration. The results were statistically analyzed by analysis of variance (ANOVA) and analysis by comparison of independent samples in order to verify the significance of the values obtained and the influence of variation of parameters. For the concentration range studied (5, 25, 50 and 100 mg L-1) the values found in the permeate concentration were all pretty low. The highest value obtained was 0.026 mg L-1 in nanofiltration test with initial concentration of 5 mg L-1 of beta-cyfluthrin in water. The results showed excellent rejections in all tests, either with isolated active ingredient or in coexistence of them, attesting rejections greater than 99,5% for both pyrethroids, under the pressure of 5 bar. The nanofiltration process had higher and better permeate fluxes than the reverse osmosis. However, regarding the effectiveness of separation, both processes showed excellent performance in the removal of pyrethroids, thus enabling the choice of these methods for treatment of wastewater which are contaminated with this kind of pesticide

Sistemas de membranas filtrantes, principalmente os de osmose reversa, estão sendo cada vez mais utilizados em diversos seguimentos de empresas (farmacêutica, tratamento de água, alimentícia e química), devido à diminuição do preço dos elementos filtrantes e da alta qualidade do produto obtido. Apesar do preço dos elementos de osmose reversa terem caído nos últimos tempos, a substituição destes continua sendo o fator mais dispendioso de um sistema de osmose reversa. A autópsia de membranas é uma técnica utilizada para investigar a causa que levou à colmatação de um elemento, contribuindo no melhoramento do pré-tratamento da água de alimentação e consequentemente aumentando a vida útil dos elementos. O presente trabalho teve como objetivo incrementar a técnica de autópsia de membranas de osmose reversa através da análise da volatilização dos principais compostos inorgânicos presentes nestas membranas, modificação na metodologia de quantificação de açúcares e proteínas, comparação de diferentes técnicas de remoção do material depositado sobre as membranas e análise da distribuição de biofilmes sobre elementos colmatados de osmose reversa. A análise dos resultados mostrou que dentre os inorgânicos, ocorreu volatilização completa do cloreto de amônio e pequena variação no composto cloreto férrico; a quantificação de proteínas e açúcares, através da fortificação das amostras, apresentou valores diferentes quando comparados com os valores obtidos diretamente da curva padrão, devido à diferença de inclinação entre as retas de fortificação e padrão; os resultados também mostraram que a trituração foi mais eficiente na remoção do material aderido quando comparado com a raspagem e a sonicação e a distribuição de biofilmes se mostrou uniforme nos dois elementos analisados. / Filter membrane systems, especially reverse osmosis, are being increasingly used in various business segments (pharmaceutical, water treatment, food and chemical) due to decrease in the price of the filter elements and high quality product. Although the price of reverse osmosis elements have fallen in recent times, the replacement of the part remains more expensive a reverse osmosis system. The autopsy of membranes is a technique used to investigate the cause that led to clogging of one factor contributing to the improvement of pre-treatment of water feeding and consequently increasing the life of the elements. This study aimed to improve the technique of autopsy reverse osmosis membranes by examining the volatilization of major inorganic compounds present in these membranes, modification the methodology for quantification of sugars and proteins, comparison of different techniques for removal of material deposited on the membranes and distribution analysis of biofilms on elements obscured reverse osmosis. The results showed that among the Inorganic volatilization was full of ammonium chloride and small variation in the compound ferric chloride, the quantification of proteins and sugars, by fortifying the samples showed different values when compared with values obtained directly the standard curve due to the difference in slope between the lines of and fortification standard, the results also showed that the blending was more efficient in removing adhered material when compared with the scraping and sonication and distribution of biofilms showed uniform the two elements analyzed.

O tratamento de efluentes industriais tem sido objeto de estudos no sentido da busca de soluções que minimizem impactos ambientais e promovam a conservação do bem natural que é a água. Nesta linha de pensamento, o presente trabalho propôs-se avaliar a viabilidade de recuperação de efluentes industriais contaminados com pesticidas do tipo piretróides em específico: a deltametrina e beta-ciflutrina. A justificativa na escolha deste tipo de componente está fundamentada na alta demanda alimentícia por parte da população mundial e o consequente acréscimo no uso dos agrotóxicos a fim de garantir a eficiência e o elevado volume de produção de alimentos. O objetivo deste trabalho foi estudar a remoção da deltametrina e da beta-ciflutrina de efluentes sintéticos aquosos por meio dos processos de osmose inversa e nanofiltração, com a utilização de membranas de poliamida. O presente estudo se justifica pelo atendimento aos padrões ambientais de concentração de piretróides no meio ambiente e reafirma o uso do sistema com membranas no tratamento de efluentes e remoção destes contaminantes. Para caracterização das membranas, foi realizado o teste de permeabilidade hidráulica, constatando diferentes linearidades de fluxo entre os dois processos, com a variação de pressão de trabalho. O desempenho dos processos foi verificado pela variação de parâmetros de meio reacional, variando a concentração dos piretróides em solução, analisando os princípios ativos isolados e também em mistura de ambos piretróides. Primeiramente se estudou a remoção da deltametrina e da beta-ciflutrina isoladamente em solução, nas concentrações de 5, 25, 50 e 100 mg L-1, sob a pressão de 5 bar. Posteriormente, avaliou-se o desempenho das membranas na remoção dos piretróides em mistura nas soluções sintéticas, com ambos os princípios ativos na concentração de 50 mg L-1, na pressão de 5 bar. Foi estudada a remoção da deltametrina e da beta-ciflutrina nos dois processos: osmose inversa e nanofiltração. Os resultados foram tratados estatisticamente por análise de variância (ANOVA) e pela análise por comparação de amostras independentes a fim de verificar a significância dos valores obtidos e a influência da variação dos parâmetros analisados. Para a faixa de concentração estudada (5, 25, 50 e 100 mg L-1) os valores encontrados de concentração de permeado foram todos consideravelmente baixos. O maior valor encontrado foi de 0,026 mg L-1 no ensaio de nanofiltração com concentração inicial de 5 mg L-1 de beta-ciflutrina em água. Os resultados apresentaram excelentes rejeições em todos os testes, seja com princípio ativo isolado ou em mistura, com rejeições maiores que 99,5% para ambos os piretróides nas concentrações testadas, sob a pressão de 5 bar. O processo de nanofiltração apresentou maiores e melhores fluxos de permeado do que a osmose inversa. Contudo, no que diz respeito à eficácia da separação, ambos processos indicaram ótimo desempenho na remoção dos piretróides, viabilizando assim, a escolha destes métodos para tratamento de efluentes contaminados com este pesticida / Treatment of industrial effluents has been the subject of numerous studies aimed at finding solutions that minimize environmental impacts and promote the recovery and / or reuse of the natural benefit which is the water. With this in mind, this study aims to evaluate the feasibility of recovery of industrial effluents contaminated with pyrethroid pesticide - in particular: the beta-cyfluthrin and deltamethrin. The justification for choosing this type of component is based on the high demand for food for the world population and consequent increase in the use of pesticides to ensure efficiency and high volume food production. The aim of this work was to study the removal of deltamethrin and beta-cyfluthrin from synthetic effluents through process of reverse osmosis and nanofiltration, with the use of polyamide membranes. This study is justified by attendance to environmental standards for pyrethroids concentration in the environment and it reaffirms the use of membranes system in wastewater treatment and in the removal of contaminants. For membranes characterization an hydraulic permeability test was performed, noting different flow linearities between the two processes, under variation of pressure. The process performance was verified by variation of parameters of reaction environment, by varying the concentration of pyrethroids in solution, examining the active ingredients alone and in mixture of both pyrethroids. First of all, we have studied the removal of deltamethrin and beta-cyfluthrin alone in solution, on concentrations of 5, 25, 50 and 100 mg L-1, under the pressure of 5 bar. Subsequently, we assessed the performance of the membranes in the removal of pyrethroid in mixture in the synthetic solutions, with both active ingredients at a concentration of 50 mg L-1, at a pressure of 5 bar. We studied the removal of deltamethrin and beta-cyfluthrin in two processes: reverse osmosis and nanofiltration. The results were statistically analyzed by analysis of variance (ANOVA) and analysis by comparison of independent samples in order to verify the significance of the values obtained and the influence of variation of parameters. For the concentration range studied (5, 25, 50 and 100 mg L-1) the values found in the permeate concentration were all pretty low. The highest value obtained was 0.026 mg L-1 in nanofiltration test with initial concentration of 5 mg L-1 of beta-cyfluthrin in water. The results showed excellent rejections in all tests, either with isolated active ingredient or in coexistence of them, attesting rejections greater than 99,5% for both pyrethroids, under the pressure of 5 bar. The nanofiltration process had higher and better permeate fluxes than the reverse osmosis. However, regarding the effectiveness of separation, both processes showed excellent performance in the removal of pyrethroids, thus enabling the choice of these methods for treatment of wastewater which are contaminated with this kind of pesticide

Orientador: Maria Regina Wolf Maciel / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-08T23:42:41Z (GMT). No. of bitstreams: 1 Perioto_FabianoRomero_D.pdf: 1193759 bytes, checksum: 59c15d9b760f3098c6e92c822d878e78 (MD5) Previous issue date: 2007 / Resumo: Neste trabalho de tese, foram realizadas a modelagem e a simulação dos processos de separação pervaporação e osmose inversa aplicados a sistemas binários. A premissa empregada foi o desenvolvimento de metodologias de predição das variáveis de processo da pervaporação e osmose inversa independentes de dados experimentais destes processos; os dados necessários para a predição destas variáveis foram propriedades fundamentais dos componentes puros da alimentação. A partir de uma revisão bibliográfica dos modelos existentes para o processo de pervaporação, foi definida uma metodologia de predição das variáveis de processo baseado no modelo solução-difusão. A etapa inicial da metodologia foi o desenvolvimento de um programa de cálculo das composições de sorção na membrana, baseado no modelo UNIQUAC e no método de contribuição de grupos UNIFAC, adaptados ao uso de polímeros. O programa foi validado pela aplicação a sistemas ideais e não-ideais sob o ponto de vista termodinâmico. Os resultados empregando o modelo UNIQUAC apresentaram boaconcordância com os dados experimentais; no caso dos resultados obtidos via UNIFAC para solventes orgânicos obteve-se um bom ajuste dos dados experimentais, mas, no caso da água, os resultados obtidos pelo modelo não foram adequados. Na segunda etapa da metodologia, foram realizados o estudo da predição do coeficiente de difusão na membrana, a partir do modelo do volume livre, seguindo a abordagem de Fick e Maxwell-Stefan; a determinação dos parâmetros necessários ao respectivo modelo; a aplicação a casos estudos e uma análise paramétrica. Os resultados obtidos concordaram bem com os dados experimentais. Com isto, a partir dos valores de sorção e coeficientes de difusão, foi elaborado um programa para a predição do processo de pervaporação; o programa foi aplicado a casos estudos citados na literatura. Foi também estudada a aplicação da pervaporação ao sistema fenol-água, considerando uma membrana de poli (dimetil siloxano) como agente de separação. Os resultados concordaram bem com os dados experimentais disponíveis e mostraram que uma melhor seletividade e performance de separação foram obtidos em concentrações de fenol na alimentação inferiores a 0,2 % molar. A etapa final do trabalho foi a elaboração de um programa para simulação do processo de osmose inversa tendo como base um modelo derivado da mecânica-estatística. A partir dos parâmetros do modelo, foram preditos a rejeição e fluxo do permeado da mistura etanol-água em uma membrana de poliamida. O coeficiente de difusão de Maxwell-Stefan em alta pressão foi predito e empregado na simulação da osmose inversa / Abstract: In this work, the modelling and simulation of pervaporation and reverse osmosis processes for binary mixtures were carried out. The development of prediction methodologies for process variables of pervaporation and reverse osmosis without the necessity of experimental data was the general guideline followed; the experimental data used in these methodologies were the fundamental properties of pure components of feed. Based on the literature review for available models for pervaporation process, a prediction methodology according to the solution-difusion model was choosen and developed. The inicial step for the methodology elaboration was the development of a software for sorption composition determination in the membrane, based on the UNIQUAC model and UNIFAC group contribution method, both suitable for polymer applications. The software was validated applying it forideal and non-ideal systems on thermodynamic viewpoint. The results obtained according to the UNIQUAC model agreed well with experimental data; in the case of the results obtained by the UNIFAC method when applied for organic solvents, it was obtained a good agreement with experimental data, but, on the other hand, for the water, the results showed that the model must be improved. In the second step of methodology development, the study of the prediction of the diffusion coefficient in the membrane according Fick and Maxwell-Stefan approaches, the determination of models parameters, the validation of the prediction method with experimental data and a parametric sensitivity analysis were carried out. The results agreed well with experimental data. So, using the sorption compositions and diffusion coeficients calculated, it was developed a software for pervaporation prediction; the software was applied for some cases of literature. It was also studied the application of pervaporation to phenol-water system using poly(dimethylsiloxane) as selective barrier. The results agreed well with available experimental data and showed that a best selectivity and separation performance were achieved for phenol concentration lesser than 0.2% molar in the feed side. The final step of this work was the development of a software for simulation of reverse osmosis process based on a mecanical-statistical model. By using the model parameters, the rejection and permeate flux of ethanol-water mixture were predicted in a poliamide membrane. The diffusion coefficient of Maxwell-Stefan in high pressure was predicted and used in the reverse osmosis simulation / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

L’utilisation du procédé d’osmose inverse (OI) pour le traitement d’effluents nucléaires aqueux pose la problématique des effets de radiolyse et de vieillissement des membranes sous irradiation ɣ. Les performances des membranes (perméabilité, taux de rétention en strontium et césium) après irradiation ɣ ont été étudiées. L’irradiation par une source externe (60Co) a été réalisée dans différentes conditions représentatives de situations réelles (0,1 à 1 MGy, à 0,5 et 5 kGy.h-1, présence ou absence d’eau et d’oxygène). Une démarche analytique innovante et complémentaire (FTIR-ATR, XPS, production de gaz et d’espèces hydrosolubles) a été mise en œuvre afin d’obtenir des informations pertinentes sur les effets de l’irradiation sur les matériaux constitutifs. La chute des performances, débutant entre 0,2 MGy et 0,5 MGy, en présence d’oxygène et d’eau (débit de dose 0,5 kGy.h-1), est liée à des scissions de chaînes localisées sur la couche active de la membrane. Les dégradations se sont révélées plus faibles en absence d’oxygène et d’eau et à débit de dose à élevé. Les performances des membranes ont ensuite été évaluées sur trois matrices aqueuses différentes représentant respectivement des effluents radioactifs issus de situation post-accidentelle, accidentelle ou procédé. Les essais menés à l’échelle laboratoire et pilote montrent que dans chaque cas, l’utilisation de l’OI est possible en choisissant des membranes et des conditions opératoires adaptées. Pour finir, le temps pour atteindre une valeur seuil de dose intégrée reçue par les membranes a été estimé grâce au logiciel RABBI : une dizaine de jours pour l’effluent accidentel, plusieurs années pour les deux autres cas. / The treatment of nuclear liquid wastes by reverse osmosis (RO) involved issues of the water radiolysis and the membrane ageing due to ɣ irradiation effects. Membrane performances (permeability, strontium and cesium retention) were assessed after ɣ irradiation. Irradiation was carried out with an external 60Co source in different conditions that simulated real used of the process (dose from 0.1 to 1 MGy, dose rate of 0.5 and 5 kGy.h-1, with or without oxygen or water). Several analytical methods were performed to evaluate irradiation effects (ATR-FTIR, XPS, gas production, water soluble species released from the membrane). The methodology developed led to relevant information due to an innovative analytical protocol. Membrane performances started dropping between 0.2 and 0.5 MGy with oxygen and water (dose rate 0.5 kGy.h-1). This shift was linked to chains scissions inside the membrane active layer. The membrane degradation was weaker without oxygen or water or at high dose rate (5 kGy.h-1). Results showed that each analysis comforted each other. Membrane performances were also evaluated with three different types of liquid effluents, representing radioactive effluents from a post-disaster situation (groundwater type), disaster situation (seawater) or process water. Experiments were carried out at lab and pilote scales. Results indicated that the treatment of each effluent was possible by RO with an adequate choice of membrane and operating parameters. Finally, the time to reach an integrated dose threshold for the membrane in real conditions was estimated with the RABBI software : a dozen of days in the case of disaster situation to several years in the two other cases.

Orientador: Valéria Maia Merzel / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-28T00:18:39Z (GMT). No. of bitstreams: 1 Belgini_DaianeRodriguesBarbosa_M.pdf: 4350336 bytes, checksum: 998807ac1631e5c151a33202b7d5f9a0 (MD5) Previous issue date: 2015 / Resumo: Com o intuito de otimizar o consumo de água do meio ambiente, o reuso de efluentes têm sido cada vez mais empregado. Dentre as diferentes tecnologias utilizadas no tratamento de efluentes para reuso, os sistemas de osmose inversa se destacam por oferecer vantagens como: economia, alta produtividade e alta eficiência na remoção de sais. Entretanto, estes sistemas estão constantemente sujeitos à contaminação por micro-organismos, o que leva à perda da eficiência e aumento nos custos operacionais e de manutenção. Neste contexto, este trabalho tem por objetivo a caracterização da diversidade bacteriana de um sistema de membranas de osmose inversa que trata efluente de uma refinaria de petróleo, a fim de determinar quais são os micro-organismos relacionados com a formação de biofilme. A diversidade planctônica do sistema, i.e., água de alimentação, foi analisada através de plaqueamento e cultivo e de bibliotecas de genes RNA ribossomal 16S. A diversidade bacteriana associada às membranas foi analisada através de fingerprinting genético (DGGE ¿ Denaturing Gradient Gel Electrophoresis) e construção de bibliotecas de genes ribossomais 16S. A partir das amostras de água de alimentação, foram obtidos 37 isolados bacterianos e 211 clones. A análise das membranas foi realizada através do sequenciamento e identificação de 13 bandas excisadas a partir do fingerprinting genético, assim como pela construção de duas bibliotecas gênicas, com 73 e 57 clones cada uma. Dentre os gêneros encontrados nas diferentes amostras, os mais representativos e com potencial para formação inicial de biofilmes foram: Acidovorax, Bosea, Methylibium, Novosphingobium, Rhizobium, Shinella, Sphingomonas, Sphingobium, Devosia, Microbacterium e Sphingopyxis. De acordo com a literatura, alguns destes gêneros são constantemente encontrados em sistemas aquáticos e são importantes na formação inicial de biofilmes em sistemas de osmose inversa. O conhecimento da diversidade de micro-organismos presentes nestes sistemas fornece subsídios para entender a dinâmica e os mecanismos de formação de biofilmes na superfície de membranas, permitindo o o desenvolvimento de estratégias de controle e remoção mais específicas / Abstract: In order to reduce the environmental water consumption, reuse of wastewater has been increasingly employed. Among the different technologies used in the treatment of wastewater for reuse, reverse osmosis system stands out because of its advantages such as economy, high productivity and high efficiency in the removal of salts. However, these systems are constantly subjected to contamination by microorganisms, which causes loss of efficiency and increase in operating and maintenance costs. In this context, this study aims to characterize the bacterial diversity of a reverse osmosis membrane system treating effluent of an oil refinery in order to determine which are the microorganisms related to biofilm formation. The planktonic diversity of the system, i.e. feed water, was analyzed by cultivation techniques and 16S ribosomal gene clone libraries. Bacterial diversity associated with membranes was analyzed through genetic fingerprinting (DGGE - Denaturing Gradient Gel Electrophoresis) and the construction of 16S ribosomal gene libraries. Approximately 37 isolates and 211 clones were obtained from the feed water samples. Analysis of the membranes was performed by sequencing and identification of 13 excised bands from DGGE gel, as well as the construction of two 16S rRNA gene libraries. Among the genera found in the samples, the most representative and with potential to initial biofilm formation were Acidovorax, Bosea, Methylibium, Novosphingobium, Rhizobium, Shinella, Sphingomonas, Sphingobium, Devosia, Microbacterium and Sphingopyxis. According to the literature, some of these genera are constantly found in aquatic systems and are important in the initial formation of biofilms in reverse osmosis systems. Knowledge of the diversity of microorganisms in these systems provides subsidies to understand the dynamics and mechanisms of biofilm formation on the surface of membranes, allowing further development of control and more specific removal strategies / Mestrado / Genetica de Microorganismos / Mestra em Genética e Biologia Molecular

Estrogen compounds are a subgroup of the environmental pollutants named Endocrine Disrupting Chemicals. It is a large group of chemicals which are capable of causing hormonal imbalance of an organism and affecting its reproductive, developmental or behavioral functions. In the environment, they are found in very low concentrations (below ng/l). This makes their detection and elimination highly problematic. The Research Centre for Toxic Compounds in the Environment (RECETOX) has been developing an experimental device which employes reverse osmosis (RO) to concentrate the trace amounts of micropollutants (e.g. estrogens). The aim is to lower the detection limit of subsequent analytical methods. RO seems to be a promising alternative to commonly used methods which are more time consuming and costly. The aim of this thesis is to create a mathematical model of RO, which would describe the process of estrogen concentration and therefore could contribute to the optimization of experimental device. The mathematical model was created in MATLAB-simulink and verified by comparison to thirteen experimental results. The solutions used to test the model were NaCl at 0.002–2 g/l and drinking water with 17-ethinylestradiol of 25 ng/l. In order to concentrate the retentate on a flat-sheet RO membrane the model achieves a mean relative error in the range of 0.9–4.9 % for NaCl and drinking water. For the concentration of estrogens the deflection is 3.6 %. Comparing the model and experimental concentration of NaCl on a spiral wound RO-membrane, the deviation is in the range of 5.9–8.7 %. So far, ratio of retentate volume from the beginning to the end of the process has been used to determine the process recovery. However, due to the results obtained in the thesis, this approach appears inaccurate. A more accurate recovery would likely be achieved by using the theoretical concentration value obtained by the proposed mathematical model. However, to increase reliability, the further measurements with estrogens are needed, and also to determine the causes of deflection of model and experimental retentate volume values at the end of the concentration

Water crises are predicted to be amongst the risks of highest concern for the next ten years, due to availability, accessibility, quality and management issues. Knowledge of the microbial communities indigenous to drinking water is essential for treatment and distribution process control, risk assessment and infrastructure design. Drinking water distribution systems (DWDSs) ideally should deliver to the consumer water of the same microbial quality as that leaving a treatment plant (“biologically stable” according to WHO). At the start of this Ph.D. program water microbiology comprised conventional culturedependent methods, and no studies were available on microbial communities from source to tap. A method combining 16S rRNA gene pyrosequencing with flow cytometry was developed to accurately detect, characterize, and enumerate the microorganisms found in a water sample. Studies were conducted in seven fullscale Dutch DWDSs which transport low-AOC water without disinfectant residuals, produced from fresh water applying conventional treatment. Full-scale studies were also conducted at the desalination plant and DWDS of KAUST, Saudi Arabia where drinking water is produced from seawater applying RO membrane treatment and then transported with chlorine residual. Furthermore, biological stability was evaluated in a wastewater reuse application in the Netherlands. When low-AOC water was distributed without disinfectant residuals, greater bacterial richness was detected in the networks, however, temporal and spatial variations in the bacterial community were insignificant and a substantial fraction of the microbiome was still shared between the treated and transported water. This shared fraction was lower in the system transporting water with chlorine residual, where the eukaryotic community changed with residence time. The core microbiome was characterized and dominant members varied between the two systems. Biofilm and deposit-associated communities were found to drive tap water microbiology regardless of water source and treatment scheme. Network flushing was found to be a simple method to assess water microbiology. Biological stability was not associated with safety. The biological stability concept needs to be revised and quantified. Further research is needed to understand microbial functions and processes, how water communities affect the human microbiome, and what the “drinking” water microbiome is like in undeveloped countries. / The research presented in this doctoral dissertation was financially supported by and conducted in collaboration with Delft University of Technology (TU Delft) and Evides Waterbedrijf in the Netherlands.

Freshwater scarcity is a dire problem for exposed human societies and natural ecosystems—a problem expected to grow worse with anticipated climate change. Reverse osmosis (RO) desalination is currently the most energy-efficient and ubiquitous desalination process used for freshwater production in water-scarce regions. The synergy of high solar radiation and significantly reduced costs in photovoltaics (PV) creates the opportunity for PV to become a dominant and sustainable solution for powering the energy-intensive process of desalination and reducing greenhouse gas emissions.While photovoltaic-powered reverse osmosis (PVRO) is a promising technological solution, several significant challenges must be further addressed to sustain high RO performance. First, the inherently intermittent nature of solar energy generation can adversely affect the freshwater conversion process and thereby decrease water recovery and quality. Furthermore, global desalination capacity is dominated by large-scale plants, whereas PVRO systems are currently limited to small-scale systems. Thus, to truly integrate renewable energy with desalination systems in an impactful way, there is a need to explore pathways for modifying the RO process to enable flexible operation on a large-scale, in response to power variability. Furthermore, the techno-economic feasibility of flexible, renewable-powered RO processes and the potential benefits that could be provided to variable renewable energy (VRE) plants and the electric grid warrants investigation. Brine minimization is another major challenge for sustainable desalination. Brine management is especially an issue for inland desalination plants. Novel approaches that are less costly and less energy intensive are needed to facilitate minimal and zero liquid discharge. To enable high-salinity desalination, several variations of osmotically assisted RO, which each surpass the pressure limitation of conventional RO, have been proposed in the literature but require further assessment. The promise of these enhanced RO approaches entails a reduction in energy consumption when compared with thermal desalination methods. The primary deliverables and novel contributions of this thesis include the development of (i) design, simulation, and cost optimization models for variable-powered, variable-salinity RO systems, (ii) module-scale, cost-optimization models for enhanced RO technologies that reduce transmembrane osmotic pressure to enable high-salinity desalination and brine minimization, (iii) examining the effects of cyclic reverse osmosis on inorganic scaling mitigation, and (iv) quantifying the availability of unconventional, alternative water sources to alleviate local water scarcity in the contiguous US. First, the techno-economic feasibility of PV-powered RO desalination plants in the Gulf region was assessed using Hybrid Optimization Model for Electric Renewables (HOMER) and Desalination Economic Evaluation Program (DEEP) to model both the power system and desalination system, respectively. Subsequently, an hourly simulation model for desalination was developed to replace the use of DEEP in the workflow. Grid-connected and off-grid cases with combinations of PV, batteries, and diesel generators were evaluated primarily by the levelized cost of electricity (LCOE) and levelized cost of water (LCOW). The shortcoming of conventional and PV-powered RO is that variable power compromises cumulative water production, which in turn increases water costs. Thus, we proposed the concept of active-salinity-control reverse osmosis (ASCRO) which enables control of the transmembrane osmotic pressure and water production in response to variable power. The ASCRO system dynamically controls energy consumption by operating across a range of feed salinity, allowing it to shift over a wide range of pump feed flows and pressures. To accomplish this, ASCRO utilizes feedwater from both low- and high-salinity sources. Enabling a dynamic power consumption profile can enhance demand-response capabilities, compensating for stressors on the grid. Moreover, ASCRO can improve the integration of renewable energy (RE) by responding to power fluctuations without compromising permeate production. This system can include on-site RE and energy storage to power the ASCRO plant and provide services to the grid. We considered the following grid-connected scenarios: 1) ASCRO, 2) ASCRO and battery storage, 3) ASCRO and photovoltaics (PV), and 4) ASCRO, battery storage, and PV. The LCOW was minimized by providing load-shifting and regulation capacity services in the California Independent System Operator (CAISO) market. We quantified that the ASCRO plant can ramp from minimum to maximum load within 84 seconds, which is adequate for participation in fast-timescale markets. The LCOW for these scenarios ranged from 49 – 59 cents/m³. We also present sensitivity analyses showing the effects of capital cost, CAISO market prices, and PV size on LCOW. To investigate alternative pathways to minimal and zero liquid discharge, low-salt rejection reverse osmosis (LSRRO), cascading osmotically mediated reverse osmosis (COMRO), and osmotically assisted reverse osmosis (OARO) were comparatively assessed via module-scale, cost optimization models to gain an accurate perspective of the performance differences between each of these configurations. We quantified the optimal LCOW of each technology for the case of desalinating feedwater at 70 g/L at 75% recovery, which would result in a brine concentration near 250 g/L, a level that allows further treatment with crystallizers. For baseline scenarios, LCOW results for OARO, COMRO, and LSRRO were 5.14, 7.90, and 6.63 $/m³ of product water, respectively, while the corresponding specific energy consumption (SEC) values were 10.31, 12.77, and 28.90 kWh/m³. A sensitivity analysis is also presented. Additionally, we sought to examine the possibility of whether adaptive RO operation could provide the added benefit of fouling mitigation. Using the Pitzer model, nucleation theory, and dissolution kinetics to guide a set of bench-scale fouling experiments, CaSO₄-NaCl solution, supersaturated with respect to gypsum, was fed through a membrane test cell to determine nucleation induction times, rates of flux decline, and scale reversal. Lastly, a geospatial analysis was conducted to estimate volumes of water deficits and potential alternative water sources for the contiguous US. Namely, wastewater effluent, brackish groundwater, agricultural drainage water, and produced water were considered in this analysis as alternatives for alleviating water scarcity. We formulated a conservative estimate of groundwater availability based on environmental flow limits. Additionally, agricultural drainage volumes were estimated based on USGS water use data. Overall, the results showed that water deficits amounted to an equivalent daily capacity of 149 million m³/day—nearly 50% more than the desalination capacity of the world in 2020. Furthermore, the total availability of alternative water sources was estimated to be between 192 – 240 million m³/day, but most of this volume was not in the same location as deficits. Thus, 58 – 65% of national water deficits would have to be alleviated via long-range transport. Additionally, the potential for integrating desalination and water reuse by interconnecting existing RO plants with wastewater treatments plants was also assessed.