Os sistemas combinados anaeróbio/aeróbio para tratamento de esgotos sanitários têm sido considerados alternativas viáveis do ponto de vista técnico-econômico em relação aos sistemas tradicionais. Este trabalho apresenta os resultados obtidos com uma nova configuração de reator, composto por uma unidade central - um reator anaeróbio de manta de lodo (UASB) modificado de 286 L, associado a um reator radial aerado de leito fixo (RRLF) de 215 L, disposto de maneira a circundar a zona de separação sólido/líquido/gás do reator UASB. A principal modificação no reator UASB foi, portanto, a incorporação, junto à sua parede externa, do RRLF. A alimentação do RRLF com o efluente do UASB dá-se através de aberturas laterais na parede do UASB, o que permitiu eliminar as calhas de coleta e sistemas de alimentação do segundo reator. Esse sistema foi alimentado com esgoto sanitário obtido da rede coletora de esgotos do campus da USP de São Carlos. Esperava-se obter remoção considerável de matéria orgânica solúvel e particulada, bem como a remoção parcial de nitrogênio. Foram obtidas eficiências médias de remoção de matéria orgânica (expressa como demanda química de oxigênio - DQO) e de sólidos suspensos voláteis (SSV), de 80% e 89%, respectivamente. Em condições de operação estável, os valores de DQO e SSV no efluente atingiram 110 mg/L e 16 mg/L, respectivamente. Observou-se, também, que o sistema apresentou grande estabilidade operacional, tendo a taxa de carregamento orgânico volumétrica atingido valores da ordem de 4,0 Kg DQO.m-3d-1. Nessas condições, o sistema atingiu eficiências de remoção de DQO e SSV da ordem de 90%. O sistema misto ensaiado mostrou ser uma configuração promissora, pois promoveu a remoção eficiente de matéria orgânica e de sólidos suspensos. Considera-se, no entanto, a necessidade de se introduzirem modificações no projeto RRLF que permitam o estabelecimento dos processos de nitrificação e desnitrificação nesse reator, uma vez que foi obtida baixa eficiência de nitrificação e, conseqüentemente, a remoção de nitrogênio foi prejudicada. / Integrated anaerobic/aerobic systems have been considered feasible alternatives concerning technical and economic aspects for treating domestic wastewaters. This paper presents the results obtained from the operation of this new reactor configuration, made up of a central unit - an upflow anaerobic sludge blanket reactor (UASB), with a working volume of 286 L, associated to a radial-flow aerobic immobilized-biomass (RAIB), with a working volume of 215 L. The RAIB reactor circles the solid/liquid/gas separation zone. The main modification in the UASB reactor concerns this association with the RAIB. The UASB effluent was distributed through openings along its side walls to the RAIB, allowing the elimination of collecting channels and feeding devices from the latter reactor. The objective of this work was to promote organic matter (raw and soluble) and nitrogen removal from domestic sewage. Organic matter (as COD) and volatile suspended solids removal achieved efficiencies of 80% and 89%, respectively. Under stable operational conditions, the system effluent presented COD and volatile suspended solids values of 110 mg/L and 16 mg/L, respectively. Efficiencies of 90% for COD and volatile suspended solids removal were achieved with a organic loading rate of 4,0 Kg COD.m-3.d-1. This integrated system has shown to be a valid configuration, efficiently removing organic matter and suspended solids from the domestic wastewater. However, contrarily to expectations based on the previous studies with RAIB, nitrification was poor. Therefore, modifications to the RAIB design must be considered for the establishment of nitrogen removing processes.

The last couple of decades have seen entrained-flow gasification of black liquor (BL) undergo an incremental process of technical development as an alternative to combustion in a recovery boiler. The ability of the technology to combine chemical recovery with the production of clean syngas renders it a promising candidate for the transformation of chemical pulp mills into integrated forest biorefineries. However, techno-economic assessments have shown that blending BL with the more easily transportable pyrolysis oil (PO) can not only increase the system efficiency for methanol production but remove a significant roadblock to development by partially decoupling production capacity from limitations on black liquor availability. The verification and study of catalytic co-gasification in an industrially-relative scale can yield both scientifically interesting and practically useful results, yet it is a costly and time-consuming enterprise. The expense and time involved can be significantly reduced by performing thermodynamic equilibrium calculations using a model that has been validated with relevant experimental data. The main objective of this thesis was to study, understand, quantify and compare the gasification behaviour and process performance of black liquor and pyrolysis oil blends in pilot-scale. A secondary objective of this work was to demonstrate and assess the usefulness and accuracy of unconstrained thermodynamic equilibrium modelling as a tool for studying and predicting the characteristics of alkali-impregnated biomass entrained-flow gasification. The co-gasification of BL/PO blends was studied at the 3 MWth LTU Green Fuels pilot plant in a series of experimental studies between June 2015 and April 2016. The results of the studies showed that the blending of black liquor with the more energy rich pyrolysis oil increased the energetic efficiency of the BLG process without adversely affecting carbon conversion. The effect of blend ratio and reactor temperature on the gasification performance of PO and BL blends with up to 20 wt% PO was studied in order to assess the impact of alkali-dilution in fuel on the conversion characteristics. In addition to unblended BL, three blends with PO/BL ratios of 10/90, 15/85 and 20/80 wt% were gasified at a constant load of 2.75 MWth. The decrease in fuel inorganic content with increasing PO fraction resulted in more dilute green liquor (GL) and a greater portion of the feedstock carbon ended up in syngas as CO. As a consequence, the cold gas efficiency increased by about 5%-units. Carbon conversion was in the range 98.8-99.5% and did not vary systematically with either fuel composition or temperature. The validation of thermodynamic equilibrium simulation of black liquor and pyrolysis co-gasifications with experimental data revealed the need to be mindful of errors and uncertainities in fuel composition that can influence predictions of equilibrium temperature. However, provided due care is to taken to ensure the use of accurate fuel composition data, unconstrained TEMs can serve as a robust and useful tool for simulating catalytic entrained-flow gasification of biomass-based feedstocks. / LTU Biosyngas (Catalytic Gasification)

Reducing energy consumption in pulp and paper refining requires a deep understanding of all the processes involved. This dissertation investigates fundamental mechanics of the low consistency mechanical refining process. Three studies investigate forces applied to wood fibers with the focus on how force profiles during bar passing events change with process variables such as fiber length and refiner load. In the first study a high resolution rotary encoder and a piezo ceramic force sensor are implemented in a 16-inch laboratory-scale low consistency refiner to explore the effect of plate gaps on bar-force profiles. The rotary encoder data is used to locate the rotor bars relative to the stator bar in which the sensor is located. Force profiles for bar passing events are registered to the position of rotor bars relative to the stator bar in which the sensor is located and mean force profiles are produced. These mean force profiles have potential to shed light on the fundamental mechanisms of mechanical refining. For large gaps, there is a late peak in the force profiles that occurs toward the end of the bar passing event. For gaps that are less than the critical gap, below which fiber cutting occurs, there is an early peak in the force profiles that occurs at the start of the bar passing event. It is hypothesized that the early peak represents the corner force and, therefore, that corner force is causal in the onset of fiber cutting. In the second study a set of piezo ceramic force sensors is implemented in a 52-inch mill-scale low consistency refiner to explore the effect of varying operating conditions on bar force profiles. Force profiles for individual bar passing events are identified based on key features in the time domain force data based on the knowledge acquired from the previous study in the pilot-scale refiner. The individual bar force profiles are classified as single peak events which feature one peak corresponding to the fiber compression force and as dual peak events corresponding to fiber compression force and the corner force. It is shown that dual peak events which are considered to represent the corner force, are present throughout the whole range of refining and increase with increased refining energy. After applying the dual peak analysis to the data from the previous study this behaviour was also found in the pilot-scale refiner data. Furthermore, it is found that different radial positions on the stator plate are subjected to different force profiles. This is thought to be due to the difference in tangential speed and a change in the fiber and floc material properties at different radial positions. In the third study the effect of refiner plate wear on bar force sensor measurements is explored by applying the dual peak analysis to long term data acquired from the mill-scale refiner. Bar passing events are analysed based on the dual peak ratio and the timing of the early peak in the dual peak events. Force measurements are evaluated over the full run time of a set of refiner plates. When comparing force profiles with refiner plate wear measurements and discharge fiber analysis, it is found that the decrease in the prevalence of the corner force correlates with the wear of the leading edge of the refiner bars, or bar rounding, for the run time of the refiner plate. This is accompanied by a decrease in plate performance which is represented by a decrease in fiber length and freeness reduction for the same refiner load. / Graduate

The multi zone fluidized bed reactor instantaneously creates several chemical/physical environments in a single reactor vessel. Effective solid circulation across zones can be achieved by tuning the reactor geometries, solid properties, and operating conditions. However, there is limited research for this innovative reactor concept beyond the laboratory scale, among which a better understanding of the complex fluid dynamics, dominating the solid circulation in different zones, is a basis. This work aims to propose a new method to capture the fluid dynamics of a pilot MZFBR by laboratory measurements with validation from theoretical analysis and simulation. Toward this goal, we first performed particle characterizations, and fluidization testing experiments in a laboratory scale fluidized bed reactor and a pilot scale multi zone fluidized bed reactor at ambient conditions to study the development of fluidization regimes. Then we compared the minimum fluidization velocity with argon and air between the experimental measurements and theoretical calculation results and proposed a modified Ergun equation, which better fits our system. Finally, we conducted computational particle fluid dynamics simulations for the pilot multi zone fluidized bed reactor with the Ergun equation and our modified equation and compared the results against previous experimental observations. Simulations display that the prediction of pressure drop in the pilot scale multi zone fluidized bed reactor with the proposed Ergun equation is similar to that of the original equation, with a relative deviation of around 3%. However, the modified equation captured the bubbling fluidization behavior as the experiment, while the Ergun equation predicted a smooth fluidization without any bubbles. The better agreements validated both our workflow of estimating the fluidization behavior in a pilot multi zone fluidized bed reactor from laboratory measurements and the simulation strategy.

Les nanoémulsions sont des formulations intéressantes pour des applications telles que les cosmétiques, les produits pharmaceutiques et les produits alimentaires. Elles peuvent être produites par des techniques à basse ou haute énergie. Dans ce travail, un procédé impliquant une pression modérée, l'émulsification membranaire par prémix a été proposé comme alternative. Des nanoémulsions huile-dans-eau (H/E) et eau-dans-huile (E/H) ont été produites avec une installation à l'échelle pilote composée d'un pousse-seringue à haute pression et d'une membrane Shirasu Porous Glass (SPG). Tout d'abord, l'influence des nombreux paramètres de procédé et de composition sur la taille des gouttelettes et la pression résultante a été étudiée avec des compositions modèles afin d'optimiser la production. Ainsi, des nanoémulsions H/E d'environ 260 nm et E/H d'environ 600 nm ont été produites avec succès. Puis, le montage a été utilisé pour produire des nanoémulsions de compositions spécifiques, des nanoémulsions H/E et E/H stabilisées avec des tensioactifs polypeptidiques et une nanoémulsion H/E adaptée à l'injection. Enfin, le procédé développé a été comparé à deux procédés à haute énergie traditionnels, le microfludiseur et les ultrasons en termes de taille des gouttelettes et de conservation d'actifs. Aucune différence entre les procédés n'a été observée en ce qui concerne la préservation de l'acif choisi. Cependant, en ce qui concerne la taille, les nanoémulsions produites par les membranes ont présenté des gouttelettes monodisperses de 335 nm par rapport aux autres procédés qui ont produit des nanoémulsions d'environ 150 nm de taille moyenne mais contenant aussi des gouttelettes de taille micrométrique détectées par diffraction laser et microscopie optique. Pour cette raison, les nanoémulsions produites par procédé membranaire conviennent également pour des applications parentérales sans étape de filtration supplémentaire / Nanoemulsions are interesting carriers for applications such as cosmetics, pharmaceutical and food. They are produced usually by low or high energy techniques. In this work, a process involving moderate pressure, premix membrane emulsification (PME) was proposed as an alternative. Oil-in-water (O/W) and water-in-oil (W/O) nanoemulsions were produced with a pilot scale set-up composed of a controlled high pressure syringe pump and Shirasu Porous Glass (SPG) membrane. First, the influence of process and composition parameters on droplet sizes and pressures was extensively studied with model compositions to optimize the production. Thus, nanoemulsions down to 260 nm for O/W and around 600 nm for W/O were successfully produced. Then, the set-up was used to produce nanoemulsions of specific compositions: O/W and W/O nanoemulsions stabilized with polypeptidic surfactants and O/W nanoemulsions suitable for injection. Finally, the set-up developed was compared to two traditional high energy processes, microfludizer and ultrasound in terms of droplet size and active preservation. No real difference between the three processes was seen on active preservation with the model active chosen. However, regarding droplet size, PME produced monodispersed droplets of 335 nm compared to the other processes which produced nanoemulsions of around 150 nm but with the presence of micron size droplets detected by laser diffraction and optical microscopy. Therefore, PME nanoemulsions are also suitable for parenterals applications with no additional filtration step required

Este trabalho fundamentou-se na concepção, desenvolvimento tecnológico, ampliação de escala e avaliação do comportamento de sistema combinado anaeróbio-aeróbio de leito fixo e fluxo ascendente, com recirculação da fase líquida, para tratamento de esgoto sanitário. O reator, em escala piloto, foi construído em formato cilíndrico e confeccionado em fibra de vidro com volume total de aproximadamente 2,5 \'M POT.3\', com intuito de desenvolver um sistema capaz de operar como única unidade de tratamento para remoção de matéria orgânica e nitrogênio, reduzindo a geração de lodo e o consumo de energia pela combinação dos processos anaeróbio e aeróbio, possibilitando o aproveitamento das vantagens de cada um e minimizando seus aspectos negativos. Os melhores resultados operacionais foram encontrados para a etapa com tempo de detenção hidráulica total (TDH) de 12 horas e razão de recirculação (r) igual a 3,0, apresentando eficiências médias de remoção de DQO, \'N\'-NTK e SST de 92 ± 3%; 68 ± 11% e 75 ± 7%, respectivamente, com valores médios efluentes de 54 ± 22 mgDQO/L, 14 ± 10 mg \'N\'-NTK/L e 70 ± 42 mgSST/L. Os valores médios de carga orgânica volumétrica (COV) e carga volumétrica de nitrogênio (CVN) removidas foram de 1,08 ± 0,04 kgDQO/\'M POT.3\'.dia e 0,06 ± 0,02 kgNTK/\'M POT.3\'.dia para esta etapa. A estabilidade operacional durante a etapa com TDH de 12 h, a alta remoção de matéria orgânica e nitrogênio, sem a necessidade de adição de fonte exógena de carbono, para promover o processo de desnitrificação, e de suplementação de alcalinidade consumida durante a nitrificação, e a reduzida necessidade de manutenção devido à tecnologia de fabricação adotada, comprovam a viabilidade técnica de utilização do reator combinado de leito fixo como unidade compacta para pequenas comunidades ou vazões afluentes, para tratamento de esgoto sanitário. / This work was based on design, technology development, scale up and performance evaluation of an up-flow combined anaerobic-aerobic fixed bed system, with recycle of the liquid phase, for treatment of domestic sewage. The pilot scale reactor was built in a fiberglass cylindrical shape with a total volume of approximately 2.5 \'M POT.3\', aiming at the development of a system capable of operate as a single treatment unit for organic matter and nitrogen removal, with low sludge production and energy consumption by the advantages of combination of anaerobic and aerobic processes. The improved operating results were found for the condition with overall hydraulic retention time (HRT) of 12 hours and recycle ratio (r) equal to 3.0, with average removal efficiencies of COD, TKN and TSS of 92 ± 3%, 68 ± 11% and 75 ± 7%, respectively, with average effluent values of 54 ± 22 mgCOD/L, 14 ± 10 mgTKN/L and 70 ± 42 mgTSS/L. The average values of removed organic loading rate (OLR) and nitrogen volumetric loading (NVL) reached 1.06 ± 0.04 kgCOD/\'M POT.3.d and 0.06 ± 0.02 kgTKN/\'\'M POT.3\'.d for this phase. The operational stability during the stage with HRT of 12 h, the high organic matter and nitrogen removal, without addition of exogenous carbon source (electron donor) to promote the denitrification process, with no supplementation of alkalinity consumed during nitrification, and the reduced maintenance due to manufacturing technology adopted, proved the technical feasibility of the combined fixed-bed reactor as a compact unit for small communities or low inflow rates, for treatment of domestic sewage.

Este trabalho fundamentou-se na concepção, desenvolvimento tecnológico, ampliação de escala e avaliação do comportamento de sistema combinado anaeróbio-aeróbio de leito fixo e fluxo ascendente, com recirculação da fase líquida, para tratamento de esgoto sanitário. O reator, em escala piloto, foi construído em formato cilíndrico e confeccionado em fibra de vidro com volume total de aproximadamente 2,5 \'M POT.3\', com intuito de desenvolver um sistema capaz de operar como única unidade de tratamento para remoção de matéria orgânica e nitrogênio, reduzindo a geração de lodo e o consumo de energia pela combinação dos processos anaeróbio e aeróbio, possibilitando o aproveitamento das vantagens de cada um e minimizando seus aspectos negativos. Os melhores resultados operacionais foram encontrados para a etapa com tempo de detenção hidráulica total (TDH) de 12 horas e razão de recirculação (r) igual a 3,0, apresentando eficiências médias de remoção de DQO, \'N\'-NTK e SST de 92 ± 3%; 68 ± 11% e 75 ± 7%, respectivamente, com valores médios efluentes de 54 ± 22 mgDQO/L, 14 ± 10 mg \'N\'-NTK/L e 70 ± 42 mgSST/L. Os valores médios de carga orgânica volumétrica (COV) e carga volumétrica de nitrogênio (CVN) removidas foram de 1,08 ± 0,04 kgDQO/\'M POT.3\'.dia e 0,06 ± 0,02 kgNTK/\'M POT.3\'.dia para esta etapa. A estabilidade operacional durante a etapa com TDH de 12 h, a alta remoção de matéria orgânica e nitrogênio, sem a necessidade de adição de fonte exógena de carbono, para promover o processo de desnitrificação, e de suplementação de alcalinidade consumida durante a nitrificação, e a reduzida necessidade de manutenção devido à tecnologia de fabricação adotada, comprovam a viabilidade técnica de utilização do reator combinado de leito fixo como unidade compacta para pequenas comunidades ou vazões afluentes, para tratamento de esgoto sanitário. / This work was based on design, technology development, scale up and performance evaluation of an up-flow combined anaerobic-aerobic fixed bed system, with recycle of the liquid phase, for treatment of domestic sewage. The pilot scale reactor was built in a fiberglass cylindrical shape with a total volume of approximately 2.5 \'M POT.3\', aiming at the development of a system capable of operate as a single treatment unit for organic matter and nitrogen removal, with low sludge production and energy consumption by the advantages of combination of anaerobic and aerobic processes. The improved operating results were found for the condition with overall hydraulic retention time (HRT) of 12 hours and recycle ratio (r) equal to 3.0, with average removal efficiencies of COD, TKN and TSS of 92 ± 3%, 68 ± 11% and 75 ± 7%, respectively, with average effluent values of 54 ± 22 mgCOD/L, 14 ± 10 mgTKN/L and 70 ± 42 mgTSS/L. The average values of removed organic loading rate (OLR) and nitrogen volumetric loading (NVL) reached 1.06 ± 0.04 kgCOD/\'M POT.3.d and 0.06 ± 0.02 kgTKN/\'\'M POT.3\'.d for this phase. The operational stability during the stage with HRT of 12 h, the high organic matter and nitrogen removal, without addition of exogenous carbon source (electron donor) to promote the denitrification process, with no supplementation of alkalinity consumed during nitrification, and the reduced maintenance due to manufacturing technology adopted, proved the technical feasibility of the combined fixed-bed reactor as a compact unit for small communities or low inflow rates, for treatment of domestic sewage.

<p> This report examines the dynamic response of a 0. 5 metre pilot scale rotating biological contactor when operated under transient influent conditions. Experimental data are presented for two modes of operation: carbon oxidation and carbon oxidation plus nitrification. During the carbon oxidation experimental runs, a 2.0 metre RBC was operated in parallel with the 0.5 metre RBC, thus allowing comparisons in the performance of the units. </p> <p> When the 0. 5 metre RBC was operated under nitrifying conditions, it was found that the effluent filterable TKN responded positively to influent variations in filterable TKN loading, TKN concentration and hydraulic loading. Transfer f unction noise models were developed which successfully predicted the time varying effluent TKN response. The response in effluent filterable TKN was predicted most precisely by influent TKN loading. Models based on influent TKN concentration and flow were not as precise in predicting effluent response. The effluent response of the 0.5 metre RBC was found to be greater than the response of activated sludge pilot units when operated at similar levels of removal. </p> <p> When the 0. 5 metre RBC was operated in the carbon oxidation 'mode, significant effluent responses were observed for carbon loading and concentration. Little correlation was found between influent flow and effluent carbon concentration. Operating under identical conditions, the 2.0 m RBC showed significant responses to carbon loading, carbon concentration and flow. </p> / Thesis / Master of Engineering (MEngr)

Η μελέτη των γεωμορφολογικών, των ιζηματολογικών, των γεωχημικών και των ορυκτολογικών διεργασιών σε ένα υποβαθμισμένο υγροτοπικό σύστημα κρίνεται απαραίτητη και αναγκαία πριν τη λήψη αποφάσεων, που αφορούν στην αποκατάστασή του, προκειμένου να διερευνηθεί η εξέλιξή του μέσα στο γεωλογικό χρόνο και να προβλεφθούν ενδεχόμενες αρνητικές επιπτώσεις από την επαναδημιουργία του τόσο στον άνθρωπο, όσο και στο περιβάλλον. Η παρούσα έρευνα εστιάστηκε στην περιοχή της αποξηραμένης Λίμνης Μουριάς (Ν. Ηλείας). Η λίμνη αυτή σχηματίστηκε πίσω από παράκτιους αμμώδεις φυσικούς φραγμούς και είχε τροφοδοσία από επιφανειακά ύδατα και θαλασσινό νερό, μέσω ενός διαύλου μήκους περίπου 400 m. Η αποξήρανσή της ολοκληρώθηκε στα τέλη της δεκαετίας του 1960 και οι νέες εκτάσεις δόθηκαν για καλλιέργεια. Σήμερα το μεγαλύτερο τμήμα της περιοχής είναι γεωργικά ανεκμετάλλευτο, λόγω της κακής ποιότητας του εδάφους. Επιπλέον καλύπτεται από σωρούς απορριμμάτων, μπάζων, ενώ υπάρχουν και αυθαίρετα ποιμνιοστάσια και κατοικίες. Οι ανεξέλεγκτες αυτές χρήσεις προκαλούν έντονη δυσοσμία της περιοχής, συμβάλλουν στην οπτική υποβάθμιση του τοπίου, τη ρύπανση των εδαφών και των υπόγειων νερών, ενώ είναι πολλές φορές πηγές επικίνδυνων μεταδοτικών ασθενειών. Αντικείμενο της παρούσας διατριβής είναι η διερεύνηση των γεωλογικών και εδαφολογικών παραμέτρων της αποξηραμένης Λίμνης Μουριάς. Η έρευνα εστιάστηκε στη μελέτη των φυσικών και μηχανικών ιδιοτήτων των ιζημάτων της περιοχής, καθώς επίσης των ορυκτολογικών και των χημικών τους συστατικών. Στόχος είναι η πληρέστερη κατανόηση των παραγόντων, που επηρέασαν το σχηματισμό και την εξέλιξη του συγκεκριμένου υγροτοπικού συστήματος μέσα στο χώρο και το χρόνο, η εκτίμηση του μεγέθους της ανθρωπογενούς επίδρασης και του βαθμού υποβάθμισης της περιοχής μετά την αποξήρανση της λίμνης, καθώς επίσης και η διερεύνηση της δυνατότητας εφαρμογής ενός ολοκληρωμένου προγράμματος αποκατάστασης και αειφορικής διαχείρισης, μέσω της εφαρμογής πιλοτικού επαναπλημμυρισμού μικρού τμήματος της περιοχής και της παρακολούθησής του. Για το σκοπό αυτόν πραγματοποιήθηκε εκτεταμένη εργασία υπαίθρου σε όλη την περιοχή της αποξηραμένης Λίμνης Μουριάς, στα πλαίσια της οποίας έγινε αναλυτική τοπογραφική και γεωλογική χαρτογράφηση, καθώς και δειγματοληψία πυρήνων ιζημάτων, σε βάθη έως και 5 m. Η περιοχή, που πραγματοποιήθηκε ο πιλοτικός επαναπλημμυρισμός, έχει έκταση 5 στρεμμάτων περίπου και η θέση της επιλέχθηκε μεταξύ των περιοχών ιδιοκτησίας του Δήμου Πύργου. Ο σχεδιασμός της πιλοτικής λίμνης και η κατασκευή της έγινε έτσι, ώστε η νέα λίμνη να εξυπηρετεί κοινωνικούς, εκπαιδευτικούς και ερευνητικούς σκοπούς, καθώς επίσης και να αναβαθμίζει την αισθητική του τοπίου της περιοχής. Για την πληρέστερη γεωλογική αποτύπωση και την επιτυχή κατασκευή της πιλοτικής λίμνης χαρτογραφήθηκε λεπτομερώς η έκταση των 5 στρεμμάτων και πραγματοποιήθηκε λεπτομερής δειγματοληψία πυρήνων ιζημάτων, σε βάθη έως και 2 m. Τα δείγματα από την περιοχή της αποξηραμένης λίμνης μελετήθηκαν ως προς τις φυσικές τους ιδιότητες, όπως υγρασία, pH, ηλεκτρική αγωγιμότητα, κοκκομετρική κατανομή και οργανικό υλικό, καθώς επίσης και ως προς τα ορυκτολογικά τους συστατικά. Ωστόσο η πλειονότητα των εργαστηριακών προσδιορισμών και αναλύσεων πραγματοποιήθηκε στα δείγματα που συλλέχθηκαν από την περιοχή πιλοτικού επαναπλημμυρισμού, καθώς έπρεπε να εξεταστεί η καταλληλότητα των ιζημάτων της περιοχής για την ασφαλή και επιτυχή κατασκευή της πιλοτικής λίμνης. Στα δείγματα αυτά προσδιορίστηκαν η υγρασία, το pH, η ηλεκτρική αγωγιμότητα, το ειδικό και το φαινόμενο βάρος των κόκκων, το πορώδες και ο λόγος κενών, η κοκκομετρική σύσταση, η συνεκτικότητα, η ικανότητα ανταλλαγής κατιόντων, οι περιεκτικότητες σε ανθρακικό ασβέστιο, οργανικό υλικό, κύρια στοιχεία και ιχνοστοιχεία (με Flame Atomic Absorption Spectrometry και Inductively Coupled Plasma-Mass Spectrometry), ολικό οργανικό άνθρακα και διαθέσιμα θρεπτικά συστατικά (με Flame Atomic Absorption Spectrometry και Continuous Flow Analyzer), καθώς και τα ορυκτολογικά συστατικά (με X-ray Diffraction). Ο αργιλικός ορίζοντας, που βρίσκεται σε βάθος περίπου 1 m από τη σημερινή επιφάνεια του εδάφους και απαντάται σε όλη την περιοχή επαναπλημμυρισμού, μελετήθηκε ως προς την υδροπερατότητά του. Επίσης εκτελέστηκαν δοκιμές στερεοποίησης και συμπύκνωσης στα ιζήματα αυτού του ορίζοντα, λόγω του ότι πρόκειτο να αποτελέσει τον πυθμένα της πιλοτικής λίμνης και το υλικό του θα χρησιμοποιόταν για την επίστρωση και στεγανοποίηση των πρανών της. Στα δείγματα που συλλέχθηκαν μέσα από την πλημμυρισμένη με όμβρια ύδατα πιλοτική λίμνη πραγματοποιήθηκαν προσδιορισμοί της υγρασίας, του pH, της ηλεκτρικής αγωγιμότητας, των περιεκτικοτήτων σε οργανικό υλικό και ανθρακικό ασβέστιο, της ικανότητας ανταλλαγής κατιόντων, των ορυκτολογικών συστατικών, των συγκεντρώσεων των κύριων στοιχείων, των ιχνοστοιχείων, του ολικού οργανικού άνθρακα και των διαθέσιμων θρεπτικών συστατικών. Στην παράκτια ζώνη της πρώην Λίμνης Μουριάς αναγνωρίστηκαν από κάτω προς τα πάνω ιζήματα του συστήματος φυσικών φραγμών Αγουλινίτσας, οργανογενείς λάσπες ελώδους ζώνης, ιζήματα λιμνοθαλάσσιου πυθμένα, ιζήματα φραγματικού πεδίου και ιζήματα του σημερινού συστήματος φυσικών αμμωδών φραγμών. Το κύριο τμήμα της περιοχής πίσω από την παράκτια περιοχή και προς την ενδοχώρα αποτελείται από λεπτόκοκκα ιζήματα ποτάμιας προέλευσης, τα οποία συνιστούν τα ιζήματα του λιμνοθαλάσσιου πυθμένα. Το βόρειο τμήμα της περιοχής αποτελείται επίσης από ιζήματα ποτάμιας προέλευσης και συνιστά το χερσαίο περιθώριο της λίμνης/λιμνοθάλασσας. Στην περιοχή επαναπλημμυρισμού διακρίθηκαν από κάτω προς τα πάνω ιζήματα του συστήματος φυσικών φραγμών Αγουλινίτσας και ιζήματα λιμνοθαλάσσιου πυθμένα. Η γενική απουσία οργανογενών ιζημάτων, με εξαίρεση αυτά της ελώδους ζώνης, δείχνει ότι στην περιοχή αυτή δεν επικράτησαν ποτέ οι κατάλληλες συνθήκες, οι οποίες ευνοούν τη συσσώρευση τύρφης σε παράκτια περιβάλλοντα, που σχηματίζονται πίσω από αμμώδεις φραγμούς. Φαίνεται δηλαδή ότι η συνεχής εισροή θαλασσινού νερού είχε ως επακόλουθο την άνοδο της στάθμης του νερού της λίμνης/λιμνοθάλασσας, γεγονός που εμπόδιζε τη συσσώρευση τυρφογενετικού υλικού, με αποτέλεσμα την παρουσία πολύ μικρών συγκεντρώσεων οργανικού υλικού στα ιζήματα της περιοχής. Η παθογένεια των εδαφών της αποξηραμένης Λίμνης Μουριάς και η ακαταλληλότητά τους για καλλιέργεια έγκειται στο γεγονός, ότι είναι μετρίως έως πολύ ισχυρώς αλκαλικά, με αυξημένες τιμές ηλεκτρικής αγωγιμότητας, που οφείλονται στις κακές συνθήκες στράγγισης της περιοχής, καθώς και στον αβαθή υφάλμυρο υδροφόρο ορίζοντα. Τα ιζήματα της περιοχής συνίστανται από πυριτικά ορυκτά, όπως χαλαζία, αστρίους, ιλλίτη, χλωρίτη, καολινίτη και βερμικουλίτη, ανθρακικά ορυκτά, όπως ασβεστίτη, δολομίτη και αραγωνίτη, και χλωριούχα ορυκτά, όπως αλίτη και συλβίτη. Στα δείγματα του φραγματικού πεδίου αναγνωρίστηκαν θειούχα (σιδηροπυρίτης), θειικά ορυκτά (ανυδρίτης) και οξείδια (αιματίτης). Όλα τα παραπάνω ορυκτά αποτελούν αλλόχθονα συστατικά των ιζημάτων της πρώην λίμνης, ενώ κάποια από αυτά σχηματίστηκαν και αυθιγενώς. Οι κλαστικοί κόκκοι προήλθαν από την αποσάθρωση και διάβρωση των Πλειο-Πλειστοκαινικών ιζημάτων, που συνιστούν τα ευρύτερα περιθώρια της λεκάνης του Πύργου, και των πετρωμάτων της υδρολογικής λεκάνης του Αλφειού Ποταμού και μεταφέρθηκαν στην περιοχή μέσω της ποτάμιας και της κυματικής δράσης. Επίσης ένα μέρος των κλαστικών κόκκων των ορυκτών στα ιζήματα της περιοχής μελέτης πιθανά μεταφέρθηκε με τον άνεμο. Τα ιζήματα, που συνιστούν τον αργιλικό ορίζοντα πάχους περίπου 1,5 m σε βάθος περίπου 1 m από τη σημερινή επιφάνεια του εδάφους στην περιοχή επαναπλημμυρισμού, είναι ανόργανες άργιλοι μέσης πλαστικότητας σύμφωνα με το σύστημα ταξινόμησης των εδαφών για μηχανικούς σκοπούς. Μελλοντικά προβλήματα επιφανειακής ολίσθησης των πρανών από τη διόγκωση των αργιλικών ορυκτών (βερμικουλίτη), καθώς και θολερότητας του νερού της λίμνης, πιθανά θα προκύψουν λόγω του ότι η συμπύκνωση της αργιλικής επένδυσης δεν έγινε με το συνιστώμενο σε τέτοιες περιπτώσεις τεχνικό εξοπλισμό (ποδαρικά). Ωστόσο δεν αναμένονται ουσιαστικά προβλήματα διαφυγών νερού τόσο από τον πυθμένα της λίμνης, όσο και από τα πρανή της λόγω της μικρής υδροπερατότητας των ιζημάτων αυτών. Από την καλή συσχέτιση της ικανότητας ανταλλαγής κατιόντων με την περιεκτικότητα σε αργιλικό κλάσμα, συμπεραίνεται ότι η μεγάλη ιοντοανταλλακτική ικανότητα των ιζημάτων της περιοχής επαναπλημμυρισμού οφείλεται σχεδόν αποκλειστικά στα αργιλικά ορυκτά και όχι στην παρουσία του οργανικού υλικού. Τα ιζήματα με τη μεγαλύτερη περιεκτικότητα σε αργιλικά ορυκτά και ολικό οργανικό άνθρακα παρουσίασαν ιδιαίτερα αυξημένες συγκεντρώσεις σε As, Co, Cr, Cu, Li, Mn, Ni, Pb και V. Οι υψηλές περιεκτικότητες των ιζημάτων της περιοχής επαναπλημμυρισμού σε αυτά τα στοιχεία δεν συνδέονται απαραίτητα με ανθρωπογενείς επιδράσεις, αλλά φαίνεται ότι καθοριστικό ρόλο στη σύστασή τους έπαιξε η χημική σύσταση του μητρικού πετρώματος. Ωστόσο πιθανή ρύπανση των εδαφών της περιοχής μπορεί να προέρχεται από την εκτεταμένη χρήση φυτοφαρμάκων στις καλλιεργήσιμες εκτάσεις, καθώς και από την ανεξέλεγκτη απόρριψη σκουπιδιών στις ανεκμετάλλευτες περιοχές. Οι τιμές των ατομικών λόγων ολικού οργανικού άνθρακα προς ολικό άζωτο δηλώνουν προσφορά οργανικού υλικού τόσο από υδρόβιους, όσο και από χερσαίους οργανισμούς. Μετά την κατάκλυση της πιλοτικής λίμνης με όμβρια νερά παρατηρήθηκε μικρή αύξηση των συγκεντρώσεων των ιζημάτων της λίμνης σε C, N, S και ολικό οργανικό C, σε σχέση με αυτές πριν τον επαναπλημμυρισμό, γεγονός που δείχνει ότι σε πολύ μικρό χρονικό διάστημα ξεκίνησε η βιολογική δραστηριότητα. Παράλληλα η αύξηση της περιεκτικότητας των ιζημάτων σε βιοδιαθέσιμο Κ, συμβάλλει στην ανάπτυξη της υδρόβιας και της ελόβιας βλάστησης της λίμνης. Συγκριτικά με τις μέσες περιεκτικότητες των ιζημάτων πριν από τον επαναπλημμυρισμό, τα επιφανειακά ιζήματα του πυθμένα της πιλοτικής λίμνης δεν παρουσιάζουν εμπλουτισμό στα ιχνοστοιχεία As, Co, Cr, Cu, Li, Mn, Ni, Pb και V. Αντίθετα οι συγκεντρώσεις τους φαίνεται να παραμένουν σταθερές ή να αυξάνονται λίγο σε σχέση με την προηγούμενη κατάσταση. Οι έντονα αλκαλικές συνθήκες (υψηλό pH), που επικρατούν στα εδάφη και τα ιζήματα της νέας λίμνης, δρουν ανασταλτικά στην κινητικότητα των ιχνοστοιχείων, αυξάνοντας το ποσοστό συγκράτησής τους στα ανόργανα συστατικά και μειώνοντας τη διαλυτότητά τους στο νερό της πιλοτικής λίμνης. Συνεπώς δεν αναμένεται ρύπανση του νερού της λίμνης από τα επικίνδυνα αυτά ιχνοστοιχεία, ούτε φυτοτοξικότητα των νέων φυτικών ειδών που θα αναπτυχθούν. Η συνεχής παρακολούθηση της χημικής σύστασης των ιζημάτων της πιλοτικής λίμνης, των φυσικών τους ιδιοτήτων, αλλά και των μεταβολών τους μέσα στο χρόνο, κρίνεται απαραίτητη για μεγάλο χρονικό διάστημα, καθώς ενδεχόμενη μεταβολή των συνθηκών που επικρατούν σήμερα, θα διαταράξει την ισορροπία του συστήματος της πιλοτικής λίμνης προκαλώντας ενδεχόμενα αύξηση της κινητικότητας των ιχνοστοιχείων και αποδέσμευσή τους στο περιβάλλον. / Before taking a decision for restoration of a degraded wetland, the study of geomorphological, sedimentological, mineralogical and geochemical processes, which contributed to the wetland’s formation and evolution, is essential and necessary, in order to assess environmental impacts from restoration. The objective of the present thesis was to study the geological and pedological features in the area of the drained Mouria Lake (Prefecture of Elia, Western Peloponnese). The interest was focused on the physical and the mechanical properties of the sediments, as well as on their mineralogical and chemical composition. The aim was a better understanding of the factors that controlled the wetland’s temporal and spatial evolution and the assessment of the degree of degradation and anthropogenic impacts after drainage. The ultimate aim was to implement an integrated restoration and rehabilitation plan of the former lake, based on the knowledge and experience that were acquired during the construction and monitoring of a pilot-scale wetland. Fieldwork included topographical and geological mapping, as well as sediment sampling, carried out all over the area of the former Mouria Lake. Physical properties such as moisture, acidity/alkalinity, electric conductivity, particle size distribution, as well as the organic and the mineral matter contents of the sediment samples from the drained lake, were determined in laboratory. The pilot-scale wetland, being approx. 0.5-ha large, was designed and constructed within the land owned to the Pyrgos Municipality with the purpose to meet mainly human (aesthetic, commercial and educational) needs. At the latter site detailed geological, topographical mapping and sediment logging and sampling were conducted, in order to study the bottom and the bank formations of the new pilot-scale wetland. On these sediment samples moisture, pH, electric conductivity, particle density, bulk unit weight, porosity and void ratio, particle size distribution, soil consistence (Atterberg limits), cation exchange capacity, calcium carbonate and organic matter contents, major and trace element contents using FAAS and ICP-MS, respectively, total organic carbon and plant-available nutrients contents and mineralogical composition applying X-ray diffractomentry, were conducted. The permeability, the consolidation and the compaction of the clay horizon, which lies c. 1 m beneath surface all over the study area, were determined, since this horizon constitutes the bottom of the pilot-scale wetland and is also used for sealing up the banks. Sediments from the wetland’s bottom were picked up, after the filling in with rainwater, and examined for moisture, pH values, electric conductivity, organic matter and calcium carbonate contents, cation exchange capacity, major and trace element contents, total organic carbon, plant-available nutrients and mineral matter contents. At the coastal zone of the former Mouria Lake, the Agoulinitsa sand-barrier islands, organogenic mud from the coastal telmatic zone, lagoonal bottom sediments, barrier flat sediments and modern sand-barrier islands occur from bottom to top. The main part of the drained area landwards, consists of fine lagoonal bottom sediments of fluvial origin, while the northern part consists of lagoonal marginal sediments also of fluvial origin. Lagoonal bottom sediments comprise the uppermost horizon of the re-flooded area, which overlies the Agoulinitsa sand-barrier islands. The lack of organogenic sediments at this area, except these at a small coastal telmatic zone, indicates that conditions did never favour peat accumulation. The continuous input of sea water into the lagoon due to the negative altitudes of the entire area of the former lake may have resulted in rising of the water level and mixing with sea water in the lagoon, which prevented peat accumulation. The medium to high alkalinity and the high electric conductivity, the latter due to the combination of poor drainage and the evaporation from the shallow brackish aquifer, resulted in soil pathogenesis and unsuitability for cultivation. The sediments at the new-wetland site consist of silicate minerals such as quartz, feldspars, illite, chlorite, kaolinite and vermiculite, carbonates such as calcite, dolomite and aragonite, and chloride minerals such as halite and sylvite. In the samples picked up from the barrier flat and telmatic zone, also pyrite, anhydrite and hematite were identified. Most of these constituents have a clastic origin, but some of them may form authigenically. The main factor controlling the clastic mineral influx is weathering and erosion of the Plio-Pleistocene formations, which constitute the hilly marginal areas, as well as of rocks transported by the Alpheios River from its catchment basin. Part of minerals deposited into the former lake, were airborne. The 1.5 m thick layer consisting of inorganic clay and lying 1 m beneath surface at the selected area, reveals a moderate plasticity. Future problems such as slope slides, clay swelling and turbidity in the water may arise in the pilot-scale wetland, because the equipment used for the construction of the wetland banks was not the appropriate one for clay liner compaction. However, the clay sediments do not allow water to escape through the bottom and the banks of the new wetland. The excellent correlation between cation exchange capacity and clay fraction content indicates that the clay minerals play an important role to the high cation exchange capacity of the sediments in contrast to the organic matter. High concentrations of As, Co, Cr, Cu, Li, Mn, Ni, Pb and V were determined in sediments with high clay mineral and total organic carbon contents. The weathering of the pre-Neogene and Neogene formations of the marginal areas is considered to be the major factor controlling the chemical composition of the sediments, but anthropogenic activities may contribute as well. The main activities taking place in the area of the drained Mouria Lake, which may result in the sediment contamination are the extensive use of fertilizers at the cultivated areas, as well as waste dumping. The atomic ratio values of total organic carbon to total nitrogen contents reveal organic matter supply both from aquatic and terrestrial plant species. The higher concentrations of C, N, S and total organic carbon of the sediments from the bottom of the pilot-scale wetland, in comparison to those before the construction of the new wetland, reveal that biological activity commenced after a quite short time. Additionally, the increase of bioavailable K content in these sediments positively affects the development of aquatic and helophytic vegetation. In comparison to the average trace element concentrations of the sediments from the pilot-scale wetland before filling in with rainwater, the bottom sediments do not reveal any enrichment in As, Co, Cr, Cu, Li, Mn, Ni, Pb and V. Strongly alkaline soil conditions decrease trace element mobility, as well as their solubility into the water. Under these conditions neither water contamination from hazardous soil trace elements nor plant toxicity are expected. Continuous monitoring of the chemical composition and the physical properties of the pilot-scale wetland sediments and their changes through time, is necessary, in order to assess and prevent a possible mobilization of trace elements and the subsequent release to the environment.

The separation of aqueous and organic mixtures with thermal separation processes is an important and challenging task in the chemical industry. Rising prices for energy, stricter environmental regulations and the increasing demand for high purity chemicals are the main driving forces to find alternative solutions to common separation technologies such as distillation and absorption. These are mostly too energy consumptive and can show limited separation performance, especially when applied to close boiling or azeotropic mixtures. Pervaporation can overcome these thermodynamic limitations and requires less energy because only the separated components need to be evaporated. This separation technology is already well established for the production of anhydrous solvents, but not yet widely distributed in the chemical and petrochemical industry due to some crucial challenges, which are still to overcome. Besides the need of high selective membranes, the development of membrane modules adapted to the specific requirements of organoselective pervaporation needs more research effort. Furthermore, only few modelling and simulation tools are available, which hinders the distribution of this process in industrial scale. In this work, these issues are addressed in a combined approach. In close collaboration with our cooperation partners, a novel membrane module for organophilic pervaporation is developed. A novel technology to manufacture high selective polymeric pervaporation membranes is applied to produce a membrane for an industrially relevant organic-organic separation task. A three step modelling approach ranging from a shortcut and a discrete to a rigorous model is developed and implemented in a user interface. A hydrophilic and an organophilic membrane are characterised for the separation of a 2-butanol/water mixture in a wide range of feed temperature and feed concentration in order to establish a generally valid description of the membrane performances. This approach is implemented in the three developed models to simulate the novel membrane module in industrial scale. The simulations are compared to the results of pilot scale experiments conducted with the novel membrane module. Good agreement between simulated and experimental values is reached.