Os desreguladores endócrinos, como o bisfenol A (BPA), são compostos encontrados na água em concentrações da ordem de μg.L-1 ou ng.L-1, sendo por isso também denominados micropoluentes. Sua presença, mesmo em baixas concentrações, pode causar prejuízos aos organismos expostos. Neste contexto, o objetivo do presente trabalho foi avaliar a remoção de BPA por membranas de ultrafiltração (UF) e osmose inversa (OI) e por carvão ativado granular (CAG). Essas técnicas têm a vantagem de não gerar subprodutos que também podem ser tóxicos. Nos estudos foram realizados experimentos para remoção do BPA através de membrana PL-1 (celulose regenerada de 1 kDa), Sy-10 (polietersulfona de 10 kDa) e membrana de OI (poliamida) reutilizada, com concentração inicial de 500 μg.L-1 de BPA. Para a membrana Sy-10, foram testados os pHs 7 e 10. Os ensaios de adsorção foram realizados com CAG (1-2mm) em frascos contendo 100 mL da solução de BPA, com 0,5 g de CAG para cada frasco. As variáveis testadas foram pH, tempo de contato e concentração inicial na ordem de mg.L-1. Adicionalmente, foi testada a concentração inicial de 500 μg.L-1 de BPA em experimento de adsorção. Os resultados obtidos mostraram que a capacidade da membrana Sy-10 para remoção de BPA foi superior, chegando a cerca de 90% de remoção, em contraposição aos 20% encontrados para PL-1. A membrana de OI apresentou remoções de cerca de 95%. A influência do pH (7 e 10) na remoção do BPA para a membrana Sy-10 não mostrou-se significativa. Nos ensaios de adsorção, analisando diferentes valores de pH, obteve-se eficiência de 93% para pH 7. Ensaios de variação do tempo de contato com CAG mostraram que o equilíbrio é atingido nos primeiros 10 minutos para a maior concentração e em 40 minutos para a menor concentração testada, de 500 μg.L-1. O estudo do efeito da concentração inicial de BPA na adsorção mostrou que a remoção aumenta com o aumento da concentração inicial do poluente. Conclui-se que tanto a adsorção em CAG quanto membranas são boas alternativas para a remoção de BPA de soluções aquosas. As duas técnicas poderiam ser usadas conjuntamente, sendo que o concentrado do processo com membranas poderia ser submetido à adsorção por CAG. / Endocrine disrupting chemicals, such as bisphenol A (BPA) compounds, are found in water at concentrations of the order of μg.L-1 or ng.L-1 is therefore also known micropollutants. His presence, even at low concentrations, can cause damage to exposed organisms. In this context, the aim of this study was to evaluate the removal of BPA by ultrafiltration (UF) and reverse osmosis (RO) membranes and granular activated carbon (GAC). These techniques have the advantage of not generating by-products can also be toxic. In the studies were performed experiments to remove the BPA by PL-1 (1 kDa regenerated cellulose), Sy-10 (10 kDa polyethersulfone) and RO (polyamide) reused membranes, with initial concentration of 500 μg.L-1 of BPA. For Sy-10 membrane pHs 7 and 10 were tested. The adsorption experiments were carried out with GAC (1-2mm) in flasks containing 100 mL of the BPA solution and 0.5 g of GAC to each vial. The variables tested were pH, contact time and initial concentration on the order of mg.L-1. Additionally, we tested the initial concentration of 500 μg.L-1 of BPA in adsorption experiment. Results showed that the capacity of Sy-10 membrane to remove BPA was higher, reaching approximately 90% removal, as opposed to the 20% found to PL-1. The RO membrane showed removal of about 95%. The influence of pH (7 and 10 ) in the removal of BPA onto the membrane Sy - 10 was not significant. In adsorption tests, analyzing different pH values was obtained efficiency from 93% to pH 7. Testing time variation of contact GAC showed that equilibrium is reached in the first 10 minutes to the largest concentration and 40 minutes to the lowest concentration tested, 500 μg.L-1. The study of the effect of the initial concentration of BPA in the adsorption showed that removal increases with increase in the initial concentration of the pollutant. It was concluded that both the GAC adsorption as membranes are good alternatives for the removal of the BPA aqueous solutions. The two techniques could be used together, with the concentrate from the membrane process could be subjected to adsorption GAC.

L'osmose inverse (OI) est actuellement le procédé le plus utilisé mondialement pour le dessalement des eaux saumâtres et de l’eau de mer. Cette thèse s'est intéressée à la simulation moléculaire de membranes d'OI afin d'améliorer la compréhension des propriétés structurales, dynamiques et de transport de l'eau et d'ions à l'intérieur de ces matériaux. La membrane d'OI étudiée dans ce travail est une membrane de polyamide aromatique, matériau le plus utilisé actuellement en OI. Dans la première partie de ce travail, une méthodologie a été développée pour construire un modèle atomique en trois dimensions d'une membrane polyamide fortement réticulé. Des simulations de dynamique moléculaire à l’équilibre (EMD) et hors-équilibre (NEMD) ont été réalisées pour étudier le comportement de l'eau et des ions Na+ et Cl- à travers la membrane. Les simulations EMD ont montré que les caractéristiques structurales de la membrane modèle étaient en bon accord avec celles d'une membrane typique d'OI. Les propriétés dynamiques et diélectriques de l'eau confinée dans la membrane ont également été étudiées et il a été montré que celles-ci étaient fortement modifiées par rapport à une phase volumique. Deux types de techniques NEMD ont été utilisés pour étudier le transport baromembranaire à travers la membrane modèle. La perméabilité à l'eau pure a été trouvée en très bon accord avec les données expérimentales rapportées dans la littérature et les deux méthodes NEMD ont révélé une très forte rétention saline, confirmant ainsi la pertinence du modèle de membrane d'OI développé dans ce travail. / Reverse osmosis (RO) is currently the leading process used worldwide for both brackish and seawater desalination. This thesis focuses on the molecular simulation of RO membranes in order to improve the understanding of structure, dynamics and transport of water and ions inside these materials. The RO membrane studied in this work is a typical polyamide RO membrane. In the first step of this work, a methodology for building a fully atomic and three-dimensional model of a highly cross-linked polyamide membrane was developed. Both equilibrium molecular dynamics (EMD) and non-equilibrium molecular dynamics (NEMD) simulations were further performed to investigate the behavior of water and ions (Na+ and Cl-) through the membrane. EMD simulations showed that the structural characteristics of the model polyamide membrane were in good agreement with those of a typical RO membrane. The dynamics and dielectric properties of water confined in the RO membrane were also studied and have shown to be dramatically modified with respect to the bulk phase. Two types of NEMD techniques were employed to investigate pressure-driven transport through the model membrane. Pure water permeability was found to be in very good agreement with experimental data reported in the literature for similar membrane materials and both NEMD methods highlighted very high salt rejection properties, thus confirming the relevance of the model membrane developed in this work.

Thin film Nanocomposite (TFN) membranes are a relatively new class of high-performance semipermeable membranes for Reverse Osmosis (RO) applications. Large scale applications of TFN membranes have not been achieved yet due to the high production cost of the nanoparticles, agglomeration of the nanoparticles in the thin polyamide matrix of the membrane, and leaching out of typically toxic inorganic nanoparticles into the downstream. In this work, these challenges are addressed by incorporation of two different nanofillers: Cellulose NanoCrystals (CNC), and surface functionalized Halloysite NanoTubes (HNT). Amine groups, carboxylic acid groups, and the first generation of poly(amidoamine) (PAMAM) dendrimers were used for functionalization of the HNT. CNC and HNT are environmentally friendly, low/non-toxic, abundant, and inexpensive nanoparticles with a unique size, and chemical properties. TFN membranes were synthesized via in situ interfacial polymerization of m-phenylenediamine (MPD) with trimesoyl chloride (TMC) and the nanoparticles. The control Thin Film Composite (TFC) membranes, and CNC and HNT based TFN membranes were characterized by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared spectroscopy (FTIR) and contact angle measurements. The antifouling capacity of CNC based membranes was investigated with a solution of Bovine Serum Albumin (BSA) as the fouling agent. Also, the leachability of the HNT from the membranes was examined by shaking the membranes in a batch incubator for 48 h, and then tracing the leached out HNT using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Separation characteristics of the membranes were studied by desalination of synthetic brackish water with a cross flow RO filtration system. It was revealed that incorporation of functionalized HNT enhanced the permeate flux without sacrificing the salt rejection (99.1 % ± 0.1 %). Also, incorporation of 0.1% (w/v) CNC doubled the permeate flux (from 30 to 63 L/m2.h at 20 bar) without compromising the salt rejection (97.8%). At the same time, leaching out of HNT from the TFN membranes was decreased as a result of the HNT functionalization and formation of covalent bonds with the TMC. Also, antifouling properties of the CNC-TFN membranes were 11% improved in comparison with control TFC membrane.

Os desreguladores endócrinos, como o bisfenol A (BPA), são compostos encontrados na água em concentrações da ordem de μg.L-1 ou ng.L-1, sendo por isso também denominados micropoluentes. Sua presença, mesmo em baixas concentrações, pode causar prejuízos aos organismos expostos. Neste contexto, o objetivo do presente trabalho foi avaliar a remoção de BPA por membranas de ultrafiltração (UF) e osmose inversa (OI) e por carvão ativado granular (CAG). Essas técnicas têm a vantagem de não gerar subprodutos que também podem ser tóxicos. Nos estudos foram realizados experimentos para remoção do BPA através de membrana PL-1 (celulose regenerada de 1 kDa), Sy-10 (polietersulfona de 10 kDa) e membrana de OI (poliamida) reutilizada, com concentração inicial de 500 μg.L-1 de BPA. Para a membrana Sy-10, foram testados os pHs 7 e 10. Os ensaios de adsorção foram realizados com CAG (1-2mm) em frascos contendo 100 mL da solução de BPA, com 0,5 g de CAG para cada frasco. As variáveis testadas foram pH, tempo de contato e concentração inicial na ordem de mg.L-1. Adicionalmente, foi testada a concentração inicial de 500 μg.L-1 de BPA em experimento de adsorção. Os resultados obtidos mostraram que a capacidade da membrana Sy-10 para remoção de BPA foi superior, chegando a cerca de 90% de remoção, em contraposição aos 20% encontrados para PL-1. A membrana de OI apresentou remoções de cerca de 95%. A influência do pH (7 e 10) na remoção do BPA para a membrana Sy-10 não mostrou-se significativa. Nos ensaios de adsorção, analisando diferentes valores de pH, obteve-se eficiência de 93% para pH 7. Ensaios de variação do tempo de contato com CAG mostraram que o equilíbrio é atingido nos primeiros 10 minutos para a maior concentração e em 40 minutos para a menor concentração testada, de 500 μg.L-1. O estudo do efeito da concentração inicial de BPA na adsorção mostrou que a remoção aumenta com o aumento da concentração inicial do poluente. Conclui-se que tanto a adsorção em CAG quanto membranas são boas alternativas para a remoção de BPA de soluções aquosas. As duas técnicas poderiam ser usadas conjuntamente, sendo que o concentrado do processo com membranas poderia ser submetido à adsorção por CAG. / Endocrine disrupting chemicals, such as bisphenol A (BPA) compounds, are found in water at concentrations of the order of μg.L-1 or ng.L-1 is therefore also known micropollutants. His presence, even at low concentrations, can cause damage to exposed organisms. In this context, the aim of this study was to evaluate the removal of BPA by ultrafiltration (UF) and reverse osmosis (RO) membranes and granular activated carbon (GAC). These techniques have the advantage of not generating by-products can also be toxic. In the studies were performed experiments to remove the BPA by PL-1 (1 kDa regenerated cellulose), Sy-10 (10 kDa polyethersulfone) and RO (polyamide) reused membranes, with initial concentration of 500 μg.L-1 of BPA. For Sy-10 membrane pHs 7 and 10 were tested. The adsorption experiments were carried out with GAC (1-2mm) in flasks containing 100 mL of the BPA solution and 0.5 g of GAC to each vial. The variables tested were pH, contact time and initial concentration on the order of mg.L-1. Additionally, we tested the initial concentration of 500 μg.L-1 of BPA in adsorption experiment. Results showed that the capacity of Sy-10 membrane to remove BPA was higher, reaching approximately 90% removal, as opposed to the 20% found to PL-1. The RO membrane showed removal of about 95%. The influence of pH (7 and 10 ) in the removal of BPA onto the membrane Sy - 10 was not significant. In adsorption tests, analyzing different pH values was obtained efficiency from 93% to pH 7. Testing time variation of contact GAC showed that equilibrium is reached in the first 10 minutes to the largest concentration and 40 minutes to the lowest concentration tested, 500 μg.L-1. The study of the effect of the initial concentration of BPA in the adsorption showed that removal increases with increase in the initial concentration of the pollutant. It was concluded that both the GAC adsorption as membranes are good alternatives for the removal of the BPA aqueous solutions. The two techniques could be used together, with the concentrate from the membrane process could be subjected to adsorption GAC.

O presente trabalho avaliou o desempenho de um sistema de pré-tratamento para água do mar constituído por um filtro lento de areia, com uma etapa prévia de filtração por um filtro de discos. O sistema demonstrou eficiência na remoção de fatores causadores de fouling em membranas de osmose reversa, removendo aproximadamente 97% dos sólidos suspensos totais presentes na água bruta, e gerando um filtrado com turbidez entre 0.1 e 0.2 UNT. As concentrações de microrganismos e AOC, principais fatores causadores da formação de biofouling, foram ambas reduzidas em cerca de 90%. Em sistemas de dessalinização de água do mar por osmose reversa, o pré-tratamento da água de alimentação constitui a principal estratégia no controle da formação do biofouling, que é gerado pelo estabelecimento de biofilmes sobre a superfície da membrana. A formação de biofouling gera impacto no desempenho do processo de osmose reversa e nos custos de operação. / This study evaluated the performance of a pretreatment system for seawater comprising of a slow sand filter, with a preliminary stage of filtration by disc filtration system. The system proved to be efficient in removing factors causing fouling in reverse osmosis membranes removing around 97% of the total suspended solids present in the raw water, and yielding a filtrate with turbidity between 0.1 and 0.2 NTU. The bacterial concentrations and AOC, main factors causing biofouling formation, were both reduced by about 90%. In seawater reverse osmosis systems, pretreatment of the feeded water is the main strategy to control biofouling, which is formed by the establishment of biofilms on a membrane surface. The biofouling formation produces an impact in the performance of the reverse osmosis process and operating costs.

The use of Reverse osmosis (RO) membranes have been significantly increasing in water desalination, and the main operational obstacle in RO desalination plants is membrane fouling. Among other solutes, dissolved biopolymers, such as polysaccharides can lead to severe membrane fouling especially with the addition of calcium ions because of the complexation formation between the surface of membrane and foulants materials. However, this complexation can also take place in the feed bulk, resulting in foulants aggregates formation. Although there are some physical techniques that can maintain the membrane performance without reducing its lifetime, only chemical cleanings are still commonly used in RO plants. In this study, a novel cleaning method is proposed to restore the membrane performance by removing the deposited foulants without reducing the membrane lifetime. The cleaning method is based on using water saturated with dissolved CO2 gas, and its principle is based on producing spontaneous CO2 bubbles due to local pressure difference leading to nucleation of bubbles throughout the membrane surface, especially at nucleation sites, which improve the cleaning efficiency. Alginic acid sodium salt was used as a model of polysaccharides foulants in presence of different concentrations of NaCl and calcium ions aiming to enhance membrane fouling, and then CO2 cleaning solution efficiency, in terms flux recovery (FR), was tested under different operating conditions and compared to other cleaning methods. Average FR of 20%±3, 25%±3 and 80%±3 for MilliQ water, a cleaning solution at pH4, and CO2 solution at 6 bar, 0.17 m/s, and 23 ̊C ±0.2 for 6 minutes were obtained, respectively. The efficiency of this novel cleaning method was also compared to direct osmosis overnight, and the average flux was comparable (about 60%±3), though that the cleaning time was significantly different. Various calcium concentrations (0-10 mM) were added in the alginate solution to study the fouling behavior in terms of the potential for bulk complexation to form cake alginate layer on the membrane surface rather than a gel layer, and the role of CO2 bubbles nucleation to remove foulants was investigated. This cleaning method can be considered as an alternative more environmentally friendly technique in RO application.

<p>As the number of water stressed regions around the world continues to growth due to a steadily increasing demand and climate change; the use of unconventional water sources, such as, brackish or seawater, through the implementation of desalination technologies has increased significantly. Reverse osmosis has established itself as the most widespread and energy efficient desalination technology, thanks to the development of high permeability membranes, high efficient pumps, and the integration of energy recovery devices; but, it still faces important challenges, such as, high specific energy consumption compared with traditional water treatment technologies, and poses environmental threats due to its significant CO₂emissions and the need of disposal of high salinity brine.</p> <p> </p> <p>The aim of this research is to address and provide solutions for two of the major challenge areas in reverse osmosis: reduction of the energy consumption and strategies to facilitate its integration with renewable energy sources to decrease its environmental impact. </p> <p> </p> <p>In chapter 2, the modeling and design of a double-acting batch reverse osmosis system is presented. A reduced specific energy consumption compared with previously proposed configurations was found. Moreover, the new design presents solutions to practical concerns that have limited the implementation of Batch reverse osmosis processes such as high start time and downtime, and permeate contamination. On the other hand, a novel hydraulic modeling is introduced to calculate the evolution of the pressure and other important parameters during the cycle.</p> <p> </p> <p>Chapter 3 presents a novel method which allows reverse osmosis plants to vary their power usage according to the energy availability, therefore, providing demand response capabilities. The effects on the energy consumption and performance of the reverse osmosis desalination facility due to the implementation of this technique are also studied. The split-salinity demand response reverse osmosis process proposed here poses as the first approach to grant demand response capabilities to reverse osmosis plants that provides energy gains and can be applied to existing plants. </p>

The island of Malta is highly reliant on fossil fuels for its power (99%), and due to climate mitigation policies implemented by EU the Maltese government is required to have 10% of its power generation from renewables by 2020. To achieve these energy goals, the Maltese government has expressed interest in investing on a Hexicon platform to produce 9% of the Maltese energy demand. The Hexicon platform is a floating structure capable of carrying a wide range of renewable energy generators. The Hexicon platform proposed for Malta is meant to have a rated capacity of 54MW distributed by vertical and horizontal wind energy converters. Nevertheless, due to the irregular nature of wind the Hexicon platform would still use diesel generators on-board as backup power; this inherently defeats the purpose of the Maltese investment, and therefore a Hydrogen backup system was proposed and investigated for its technical and economic viability. A literature study was carried out on renewable hydrogen system in order to familiarise with the type of markets and the best way to apply the technology to the scenario at hand. Four markets were established, small-scale, transportation, stand-alone power systems, and large buffering systems; the large buffering system is the most appropriate for the study, and taking this type of system into account, the most appropriate hydrogen generation and utilisation system were then identified. It was established that the system is composed of three parts, electrolyser, storage tanks and fuel cells stacks. However, an additional water purification system is necessary; this is due to the fact that the Hexicon platform will be located offshore, and salt water is not appropriate for the electrolyser. A literature study was then performed to identify the most appropriate equipment for each stage of the process; it was established that a Reverse Osmosis (RO) system will be used to purify the water, an alkaline electrolyser will be used to generate the Hydrogen, the Hydrogen will then be stored in pressure vessels (at 30bar), thus also requiring compressors, and the recovery of energy will be performed by a proton exchange membrane (PEM) fuel cell (FC) stack. A study was carried out to establish the models to use for each equipment, and based on the hourly demand for Malta, as well as the hourly winds, a first estimate of the size of each equipment was established. The system model was developed in the HOMER software, which unfortunately did not model the desalination plant. The Hexicon (in the design considered in this study) is not able to provide Malta with 9% of the energy demand; this was mainly due to the low wind conditions. In addition to this, it was understood from the literature study that a hydrogen system backup system, i.e. a buffering system, would not be applicable to the scenario initially proposed in this thesis due to the low renewable energy penetration, and also due to the fact that the Hexicon would be connected to the grid, rendering such a system defunct. A micro-grid scenario was assumed and developed. This scenario tried to assess how low the demand would need to be in order to make a hydrogen project feasible. Different percentages were tried and the only one that met the constraints was one with 1.1% of the Maltese demand. The system would consist of a 3MW Fuel Cell, a 4.5MW electrolyser, and hydrogen storage for 10.5tonnes. The NPC of this system would be approx. 130 Million €, with an initial investment of approx. 71 Million €, LCOE of 0.257€.kWh-1, and a Hydrogen cost of approx. 20€.kg-1. While other economic indicators show viability, for example, a short payback time of 3.5 years based on the revenue from the excess electricity, the cost of hydrogen suggests that it is too expensive.

Anammox is one of the main processes discovered quite recently for removal of ammonium from wastewater. Anammox process is cost effective, in that low energy and carbon source is needed. Partial nitritation is a perquisite for anammox in wastewater treatment for removal nitrogen and therefore partial nitritation/Anammox technology is studied substantially and applied in full-scale. However, the technology at present can only be used to treat high rich ammonium streams. Application of Anammox for treatment of low ammonium wastewater is not possible because of low yield of Anammox bacteria. The study aimed at devising strategies for using the Anammox technology to treat wastewater streams with low concentration of ammonium nitrogen. The objective was to get systems that could concentrate ammonium from low ammonium waste streams, so as to be able to treat it with partial nitritation/Anammox process. Two methods were used to concentrate ammonium: ion exchange and reverse osmosis. Ion exchange method was used to concentrate UASB effluents of about 24 - 40 mg NH4-N/l to 188 - 367 mg  NH4-N/l respectively which is about 9 times the initial concentrations. At VRF 5, 163 mg  NH4-N/l concentrate was attained from 41.8 mg  NH4-N/l RO feed. Results also showed that concentrates from both methods are able to be treated with partial nitritation/Anammox technology. However it took more than 32 hours to complete treatment of ion exchange concentrates while it took less than 24 hours to finish the partial nitritation/Anammox process of RO concentrates. The longer time taken can be attributed to high salinity of the concentrates which is as a result of NaCl which was used for regeneration in ion exchange process. Both ion exchange and reverse osmosis are viable methods for concentrating ammonium from UASB effluents. Dissolved oxygen was very important factor that influenced the biological process.

Activated carbon (AC) systems and reverse osmosis (RO) systems are commonly used point-of-use (POU) water filtration systems as the last barrier to remove trace-level contaminants in tap water to protect human health. Limited studies have been done to evaluate trace-level manganese and uranium removal in tap water. Additionally, undesired microbial growth in POU systems may reduce treatment efficiencies of POU systems and limited studies have been done to evaluate microbial growth potential in POU systems. The overall research objective of this study was to systematically evaluate the removal of metals and assimilable organic carbon in POU systems. AC systems were operated to 200% of their designed treatment capacities and RO systems were operated for three weeks. The results indicated that AC systems were generally ineffective to remove metals in drinking water, while metals were effectively removed in RO systems. The results showed that calcium and magnesium were not effectively removed in AC systems with removal efficiencies of less than 1%. Various factions of iron were removed with its removal efficiencies in AC systems ranged between 61% and 84%. Copper was effectively removed in AC systems with removal efficiencies greater than 95%, which was possibly related to its low influent concentration in drinking water (<30 μg/L). Both manganese and uranium were ineffectively removed from AC systems. Different from AC systems, RO systems were consistently effective to remove all metals. Calcium, magnesium, iron, and copper were all removed with removal efficiencies greater than 98%, while removal efficiencies of manganese and uranium in RO systems were above 95%. Assimilable organic carbon was effectively removed from all AC and RO systems and high variability of AOC removal efficiencies were observed, which may be attributed to the heterogenicity of biofilm and microbial growth in POU systems. The new knowledge generated from this study can help improve our understanding of emerging contaminant removal in POU systems and develop better strategies for the design and operation of POU systems to remove emerging contaminants in drinking water and mitigate their health risks to humans.