Water colour is the naturally occurring yellow-brown 'tea like' discolouration which can be observed in freshwaters, and is typically composed of high molecular weight organic carbon. Water discolouration is a major problem for the water industry as over the past 30 years, water colour release has more than doubled, greatly increasing treatment costs and making land management a more feasible option for improving water quality. This project was developed in conjunction with Yorkshire Water Plc, to investigate the mechanisms of water colour production, and the implications that these mechanisms have for land management to improve water quality. In particular, the study aimed to identify the key relationships between drainage water quality and quantity, soil processes and vegetation type that are pivotal to the understanding of water discolouration.

Three iron oxide materials have been studied for uptake of three anions (arsenate, phosphate and fluoride) and a cation (cadmium) from aqueous solutions. Two of the materials were produced using original procedures developed at Loughborough University. The former material was conditioned by a controlled freeze-thaw procedure to enhance granularity and the latter was air-dried at room temperature. Their capacities were compared with a commercially available material supplied by GEH Wasserchemle, Germany. Pore size distributions and specific surface area values were determined by N2 analysis at 77 K. All samples possessed a reasonable specific surface area, in the range 200-300 m2/g and were mesoporous. Samples produced at Loughborough University also contained some macropores, evidence of a more amorphous structure or lack of pH control during production. X-ray diffraction indicated that all samples had some b-FeOOH present and that the chloride content and production pH affected the material crystallinity. Crystallinity increased with increasing chloride content and a higher production pH resulted in the presence of more than one phase. Chemical characterisation was also completed on all three samples. The point of zero net proton charge and isoelectric point for each material was obtained by potentiometric batch titrations and zeta potential measurements respectively. The difference in these values increased with a higher chloride content and all samples studied possessed a positive surface at low pH and negative surface at high pH. These parameters were not greatly affected by the background electrolyte concentration, implying that the background electrolyte is not specifically adsorbed. However, arsenate and phosphate appeared to be specifically adsorbed as the isoelectric point decreased. The uptake capacities for arsenate, phosphate. fluoride and cadmium of all three samples were obtained by measuring batch isotherms at 25 degrees C. The pH range was 4-9, using various initial concentrations up to a maximum of approximately 30 uM. For all anionic species studied, the capacity decreased with increasing pH, and the reverse trend was noted for cadmium. The Langmuir model provided a good fit for the anionic isotherms and the Freundlich model for the cationic isotherms. The materials studied possessed a markedly higher capacity for fluoride than arsenate and phosphate, with an intermediate capacity for cadmium. This indicates that fluoride is attached to the surface via monodentate (single) bonds, whilst both arsenate and phosphate are primarily attached to the surface via bidentate (two) bonds. Cadmium is probably bound by both these mechanisms. The effect of competing anions on arsenic uptake capacity was determined using mini-column experiments of binary (arsenate-fluoride, arsenate-Phosphate and phosphate-fluoride) and ternary (arsenate-fluoride-phosphate) mixtures. Arsenate removal was strongly affected by the presence of phosphate, but was only slightly lower in the presence of fluoride. (Continues...).

Η παρούσα διπλωματική εργασία πραγματεύεται την αυτοματοποίηση του βιολογικού σταθμού καθαρισμού της εταιρείας «Αλουμίνιον της Ελλάδος», από τη μελέτη του αυτοματισμού μέχρι και την υλοποίησή του. Η εργασία αυτή εκπονήθηκε στην εταιρεία «Αλουμίνιον της Ελλάδος» στα Άσπρα Σπίτια Βοιωτίας. Σκοπός είναι ο εκσυγχρονισμός του βιολογικού σταθμού της εταιρείας, ώστε η λειτουργία του σταθμού να είναι πλήρως αυτοματοποιημένη και ελεγχόμενη από το σύστημα του αυτοματισμού πέρα από τον ανθρώπινο έλεγχο. Αρχικά μελετήθηκε ο τρόπος λειτουργίας του βιολογικού σταθμού ώστε να γίνει ο προγραμματισμός του αυτοματισμού που θα ελέγχει τη λειτουργία του. Στη συνέχεια δημιουργήθηκε ένας βασικός προγραμματισμός ώστε όλος ο αυτοματισμός να ακολουθεί ένα μοτίβο για πιο εύκολη κατανόηση και έλεγχο του προγράμματος του αυτοματισμού. Επιπρόσθετα καταγράφηκε το υλικό προς αυτοματοποίηση του σταθμού και οι είσοδοι και έξοδοι του προγράμματος. Σε αυτό το βήμα το τελικό στάδιο περιλάμβανε την κατάρτιση του προγράμματος λειτουργίας του αυτοματισμού. Το επόμενο βήμα ήταν να εγκατασταθεί ο εξοπλισμός του υλικού και να γίνουν οι κατάλληλες συνδέσεις των συσκευών στην κεντρική μονάδα επεξεργασίας του ελεγκτή(PLC). Τέλος σχεδιάστηκε η απεικόνιση της εγκατάστασης σε σύστημα SCADA και έγιναν οι απαραίτητες συνδέσεις του συστήματος αυτοματισμού με το πρόγραμμα SCADA ώστε να είναι δυνατή η απεικόνιση της λειτουργίας του βιολογικού σταθμού σε πραγματικό χρόνο καθώς και ο έλεγχος ή τροποποίησή της. / The following dimploma thesis deals with the automation of the biological purification station of the company “Aluminium of Greece”, starting from the study of the automation to its implementation. This thesis was developed at the facilities of “Aluminium of Greece”, in Aspra Spitia Voiotias. Its purpose is the modernization of the biological purification station, in order of a fully automated function as well as controlled by the automation system beyond the human control. Initially, the function of the biological purification station was analyzed to help programming the automation system, that controls its function. The next step was the creation of a basic program to be used as a pattern for the whole automation. The result was to be easier to understand, control and fix any problem of the automation program. Subsequently, all the devices to be connected to the automation system were recorded and a list of inputs and outputs was created. The final stage of this step consisted of creating the full program of the automation.. Thereafter the required equipment was installed and all the devices to be automated were connected to the programmable logic controller (PLC). Finally, the display of the installation was designed in a SCADA system and all the necessary connections of the SCADA system with the facility were made. With the completion of this step the engineer is now able to watch the function of the biological purification station in real time, control it and make all the necessary modifications if required.

Pollution of water by herbicides and heavy metals has caused world wide concern because of the adverse effects of these pollutants on the environment, humans and wildlife. This has resulted in tighter legislation being imposed on the levels of these pollutants in drinking water. For example, the European Union (EU) has set the legislation in the drinking water Directive Admissible Concentration for a single herbicide to a maximum of 0.1 ppb. Despite the tight environmental pollution controls, isolated cases of pollutants exceeding their limits are still encountered. This would suggest that research towards the efficient and effective removal of these pollutants will be an on-going process. In this study, sorption of copper and some selected herbicides e.g. atrazine, benazolin and 2,4-dichlorophenoxyacetic acid (2,4-D) was undertaken on a conventional activated carbon and its modified series. A low level detection method was developed using High Performance Liquid Chromatography (HPLC) and this system was used to quantify the sorption capacity of the herbicides. In order to understand the sorption mechanism of the targeted pollutants, physical and chemical characterisation of the adsorbents was undertaken using a variety of techniques. These include, Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FT-IR) method, pore size distribution and surface area measurements, elemental analysis, sodium capacity determination, zeta potential and pH titration. The sorption data were presented and analysed by conventional adsorption isotherms. Sorption of the herbicides was favoured on carbon samples with least oxygen content while the uptake of copper was strongest in oxidised carbons. Kinetic experimental data were analysed by a pseudo second order model and the Boyd kinetic model. Molecular structural configurations and the physico-chemical properties of the adsorbent played a crucial role in the sorption behaviour of the herbicides.

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La demande croissante en eau nécessite l’exploitation de certaines sources ferrugineuses. Cependant la présence du Fe(II) dissous induit des problèmes d’ordre esthétique et organoleptique. L’électrocoagulation (EC), en tant que procédé substitut de la méthode conventionnelle, a prouvé son efficacité pour l’élimination du fer. En revanche, le mécanisme de déferrisation par EC reste peu connu et non maitrisé. La difficulté de l’étudier provient de l’intervention simultanée de plusieurs phénomènes. Les travaux de cette thèse ont de ce fait pour objectif d’apporter une meilleure compréhension du mécanisme d’élimination du Fe(II) par EC. Ainsi, différentes méthodes d’élimination du fer et des techniques d’analyses du liquide et du solide ont été exploitées. Au moyen d’une unité à recirculation forcée de la solution avec des électrodes en aluminium, la technique d’EC parvient à éliminer 97% d’une solution de 25 mg/L du fer. La quantité optimale d’énergie est de 0,21 kWh/m3. Des essais en milieu anoxique ont montré que la réduction du fer ionique par adsorption sur les flocs de Al(OH)3 est faible (18%). Par oxydation-précipitation à pH 6,5, le Al(OH)3 catalyse la réaction d’oxydation. Cet effet est plus prononcé en présence des ions chlorure qu’en ions sulfate. La spéciation associée à la modélisation cinétique ont permis d’apporter des explications sur le mode d’action de ces ions. Cependant, les expériences par EC en milieux anoxique et oxygéné montrent que la part de l’oxydation dans l’élimination du fer est négligeable pour les pH de travail. Les calculs thermodynamiques au voisinage des électrodes permettent de proposer la précipitation de Fe(OH)2, comme mécanisme prédominant d’élimination du fer par EC. La présence des carbonates réduit la performance du système par la réduction de la précipitation de Fe(OH)2 suite à la diminution du pH local et le Fe2+ libre par formation des complexes du Fe(II) / Water scarcity in some areas requires the exploitation of some ferruginous sources. However, the presence of Fe(II) induces aesthetic and organoleptic problems. The electrocoagulation (EC), as an alternative process of the conventional method, proved its efficacy for iron removal. Nevertheless, the iron removal mechanism in EC process remains unstudied and still unclear. The simultaneous involvement of several phenomena makes difficulties to study the system. This thesis aims to provide a better understanding of the mechanism of Fe(II) removal by EC and to highlight the phenomena that are most likely. Thus, different methods of iron removal and liquid and solid analysis techniques have been used. By means of a forced recirculating unit, EC's technique with aluminum electrodes reduce the dissolved iron of 25 mg Fe(II)/L - solution by about 97% with an optimum energy amount of 0,21 kWh/m3. Anoxic experiments showed that the reduction of ionic iron by adsorption on Al(OH)3 flocs is negligible (18%). Oxidation-precipitation experiments showed that at work pH 6,5, Al(OH)3 catalyzes the oxidation reaction. The catalytic effect is more pronounced in the presence of chloride ions than in sulfate ions. Fe(II)-speciation associated with kinetic modeling have allowed to explain of the mode by which these ions acts on the oxidation reaction kinetics. However, EC experiments in anoxic and oxygenated media show that the proportion of oxidation in iron removal is insignificant for work pH. Thermodynamic calculations allowed to propose the precipitation of Fe(OH)2 in the vicinity of the cathode as the predominant mechanism of iron removal by EC. The presence of carbonates affects the performance of the process by reducing the precipitation of Fe(OH)2; this was attributed to the decrease of the local pH and the free Fe(II) amount by Fe(II)-complexes formation

Monodisperse titanium dioxide (TiO2) nanoparticles were synthesized by a novel freeze-drying process herein called lyophilization. The process of lyophilization is described in detail. The materials were characterized by scanning electron microscopy SEM) including energy dispersive x-ray spectroscopy (EDXS), high resolution transmission electron microscopy (HRTEM), x-ray diffraction (XRD), Raman spectroscopy and UV-Vis-IR spectrophotometry. The TiO2 nanoparticles have narrow size distribution, mono-disperse, strained with most of the characteristics showing presence of the four phases of TiO2 thus: anatase, brookite, rutile with each lyophilization process producing its own phase mostly controlled by pH and precursor concentration and anneal/calcining temperatures. With specific reference to HRTEM, Raman spectroscopy results and XRD, it was found that the Scherrer equation, the Williamson-Hall method and others of similar nature were not enough to explain the strain and the grain sizes of these particles. Therefore the Williamson-Hall method was revised to properly explain the new results. The obtained TiO2 nanoparticles were used in three applications: (1) gas sensing (2) degradation of organic water-borne pollutants using methylene blue as an indicator (3) anti-bacterial activity. / Physics / D. Phil. Physics)

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / A novel technology in the treatment of river water, which involves an electrochemical treatment technique to produce domestic or drinking water is being investigated using aluminium and iron electrodes in an electrochemical circuit. Coagulation and flocculation are traditional methods for the treatment of polluted water. Electrocoagulation presents a robust novel and innovative alternative in which a sacrificial metal anode treats water electrochemically. This has the major advantage of providing mainly active cations required for coagulation and flocculation, without increasing the salinity of the water. Electrocoagulation is a complex process with a multitude of mechanisms operating synergistically to remove pollutants from the water. A wide variety of opinions exist in the literature for key mechanisms. A lack of a systematic approach has resulted in a myriad of designs for electrocoagulation reactors without due consideration of the complexity of the system. A systematic, holistic approach is required to understand electrocoagulation and its controlling parameters. An electrocoagulation-flotation process has been developed for water treatment. This involved an electrolytic reactor with aluminium and/or iron electrodes. The water to be treated (river water) was subjected to coagulation, by Al(III) and Fe(II) ions dissolved from the electrodes, resulting in floes floating after being captured by hydrogen gas bubbles generated at the cathode surfaces. Apparent current efficiencies for AI and Fe dissolution as aqueous Al(III) and Fe(II) species at pH 6.5 and 7.8 were greater than unity. This was due to additional chemical reactions occurring parallel with electrochemical AI and Fe dissolution: oxygen reduction at anodes and cathodes, and hydrogen evolution at cathodes, resulting in net (i.e. oxidation plus reduction) currents at both anodes and cathodes. Investigation results illustrate the feasibility of ferrous and aluminium ion electrochemical treatment as being a successful method of water treatment. Better results were achieved under conditions of relatively high raw water alkalinity, relatively low raw water turbidity, and when high mixing energy conditions were available.

La contamination des ressources en eaux souterraines par une phase organique non miscible à l'eau couramment appelée NAPL (Non Aqueous Phase Liquid) constitue aujourd'hui un défi scientifique majeur compte tenu de la durée de vie d'un tel polluant. Bien que l'activité bactérienne (généralement présente sous forme de biofilm) joue un rôle crucial dans le devenir à long terme de ces effluents, peu d'études existent à l'heure actuelle sur son impact dans des conditions multiphasiques (i.e., à proximité de la source). En effet, dans la zone saturée, sous l'action des forces capillaires, le NAPL se retrouve souvent piégé, en effet, sous forme de «gouttelettes» au niveau des pores. Ce comportement spécifique au polluant modifie la dynamique du système biofilm/milieu poreux saturé et d'importantes questions restent encore ouvertes : accessibilité du polluant, modification de la tension interfaciale, production de biosurfactant, effet de toxicité (inhibition de la croissance bactérienne). Pour tenter de répondre à ces questions, nous avons adopté une approche aussi bien théorique qu'expérimentale. L'approche théorique porte sur le développement d'un modèle macroscopique décrivant le transport multiphasique en milieu poreux pour un système eau/NAPL/biofilm. Elle repose sur la méthode de prise de moyenne volumique, appliqué aux équations décrivant le couplage écoulement/transport à l'échelle du pore, permettant d'effectuer le changement d'échelle et dériver un modèle à deux équations. Le modèle est établit sous les hypothèses d'équilibre de masse local à l'interface fluide/biofilm et les contraintes associées à ces hypothèses ont étés définies. L'influence des caractéristiques microscopiques (arrangement des grains, fraction volumique du biofilm, distribution des blobs de NAPL, mouillabilité) sur les propriétés effectives du milieu (coefficient de dispersion, coefficient d'échange de masse) est discutée au travers des résultats issus des simulations. Ensuite, le modèle macroscopique a été comparé avec succès à la simulation numérique direct à l'échelle du pore pour la géométrie 2D complexe considérée. Quant à l'approche expérimentale, elle consiste à étudier le transport et la biodégradation du toluène en présence des bactéries Pseudomonas Putida F1 à l'aide d'un milieu poreux transparent 2D (micromodèle). Premièrement, nous avons étudié la dissolution du toluène résiduel sans bactéries et des courbes de dissolution du toluène ont été obtenues. Les résultats de dissolution du toluène en condition abiotique ont été comparés avec succès aux résultats du modèle théorique. Ensuite, l'étude expérimentale en micromodèle a porté sur la dissolution du toluène en condition biotique. Les résultats de ces études (courbes de dissolution et évolution de la saturation résiduelle) ont montré un impact significatif de la présence des bactéries sur les processus de dissolution par comparaison au cas abiotique. / Contamination of groundwater resources by an immiscible organic phase commonly called NAPL (Non Aqueous Phase Liquid) represents a major scientific challenge considering the residence time of such a pollutant. Although bacterial activity (usually in the form of biofilm) plays a crucial role in the long term fate of these effluents, very few works are focused on the study of such processes in multiphase conditions (oil/water/biofilm systems). The NAPL often gets trapped, in fact, under the action of capillary forces in the saturated zone in the form of «droplets» within the pores. This specific pollutant behavior changes the dynamics of biofilm /saturated porous medium system where important questions remain open: accessibility of the pollutant, changes in interfacial tension, biosurfactant production, toxicity effect (inhibition of bacterial growth). Modeling the transport of chemical species in the presence of bacteria is an extremely complex issue in terms of scale. We will use an experimental and theoretical approach to address these questions. In this thesis, we developed a macroscopic model describing multiphase transport in porous media for a water/NAPL/biofilm system. A volume averaging method has been applied here to the equations at the pore scale to make the upscaling and derive the model. This two-equation model is established under the assumptions of local mass equilibrium at the fluid/biofilm interface and the constraints associated with these assumptions were defined. The effect of microscopic features (arrangement of grains, volume fraction of the biofilm, distribution of NAPL blobs, wettability) on the effective properties of the media (dispersion coefficient, mass exchange coefficient) is discussed through some results from simulations. Subsequently, the macroscopic model has been successfully compared with the direct numerical simulation at pore scale for a 2D complex geometry. The experimental approach consists of studying transport and biodegradation of toluene in the presence of bacteria Pseudomonas Putida F1 using a flowcell. First, we studied the dissolution of toluene in abiotic conditions and toluene dissolution curves were obtained. The results of toluene dissolution in abiotic conditions were compared with success the results of the theoretical model. Finally, an experimental study in flowcell on the dissolution of toluene under biotic conditions was performed. The results of these studies (dissolution curve and evolution of toluene saturation) showed a significant impact of the presence of bacteria on the dissolution process compared to the abiotic case.