Zeolites were used in this study to remove two types of non-radioactive ions (Cobalt-59 and Strontium-89) from wastewater. This was designed to model the use of ion-exchange technique to remove radioactive Co-60 and Sr-90 from low level wastewater from Al-Tuwaitha site. Al-Tuwaitha site is a nuclear research in Iraq was used for radio-medical and radio-chemical purposes before 1990. In this study, hierarchical microporous/macroporous structures were developed to overcome the diffusivity problem using zeolite. Diatomite and carbon were used to prepare the composite adsorbents by incorporating them with three types of zeolites (A, Y and clinoptilolite). From the XRD, SEM and EDAX measurement it was confirmed that successfully prepared of Iraqi palm tree leafs-Clinoptlolite (IPClinp) and Tamarind stones-Clinoptilolite (TSClinp) composites were obtained in this study as there is no evidence in literature of this being carried out before. The carbons were prepared successfully through the Pyrolysis method for 2h at 900°C in an inert atmosphere from two types of raw waste plant materials of Iraqi Palm Tree leafs (IP) and Tamarind stones (TS). For both types of carbons, the SEM images show organised porosities in different shapes. A third material used as a zeolite scaffold was diatomite (Celatom FW-14) a readily available natural material (dead algae).A hydrothermal treatment was used to build the hierarchical structure of zeolite onto carbon and diatomite materials, the scaffolds were seeded with nano-zeolite crystals prior to the treatment and thereafter mixed with the zeolite gel composition mixture in a stainless steel autoclave. Zeolite seeds were prepared using ball mill method to reduce the particle size of the commercial zeolite to sub-micron range for each type of zeolite. The surface area, morphology, element compositions and structure for each type of zeolite and composite material were characterised using BET method, SEM, EDAX and XRD. The amounts of each type of zeolite on the carbon composites were determined using TGA while that of the diatomite composite was determined by gravimetric analysis. The results show that each type of zeolite was successfully deposited and uniformly organised onto the surface of all support materials. All pure zeolites and composite materials were successfully tested to remove Co2+ and Sr2+ ions from aqueous solutions. It was found that the composite materials had higher ability to remove both ions relative to the pure zeolites. This increase is attributed to the deposition of zeolite (microporous) onto the macroporous structure (carbon and diatomite) which increased the flow accessibility within zeolite in the hierarchical structured composites. Comparison of the removal between the two metal ions indicates that all of the materials had higher uptake for Sr2+ than Co2+ ions. The highest adsorption capacities were realised with Tamarind Stone–ZeoliteA (TSA) in the order 120mg.gz-1and 290mg.gz-1 for Co2+ and Sr2+ ions, respectively. The effect of the experimental variables shows increasing uptake with increasing pH and initial ion concentrations while it decreased with increasing the solution temperature. The Co2+ loaded composites was subjected to vitrification process at 12000C for 2h. The encapsulated composites were leached for 90 and 120 days and no significant Co2+ was recorded in the leached solution. The results show that the composite materials can be used effectively to remove the radioactive ion of Co-60 and Sr-90 ion as they display the same chemical behaviour as Co-59 and Sr-89 studied in this work.

Efficient and economic treatment of low concentration organic pollutants in water, wastewater or industrial process streams is normally very difficult to achieve. Activated carbon has been widely used for contaminant adsorption, but there are problems associated with its regeneration. In this work, a novel, non-porous, highly-conducting graphite intercalation compounds material (GIC) is used. The use of such an adsorbent can significantly reduce the time required to achieve both equilibrium and electrochemical regeneration. This character allows the design of an innovative treatment process that can adsorb contaminants and electrochemically regenerate itself simultaneously within a single unit. A novel liquid-lift reactor for water treatment by an adsorption and electrochemical regeneration process is developed in this work. Batch experiments are carried out to determine the adsorption kinetics and equilibrium isotherm of adsorption Acid Violet 17 onto the GIC adsorbent. The experimental kinetic data are analyzed using the pseudo-first order, pseudo-second order, intra-particle diffusion and three-stage kinetic models. The linear pseudo-second order model offers the highest r2 correlation coefficient. The experimental isotherm data are analyzed using Langmuir, Freundlich and Tempkin isotherm models. The non-linear Langmuir model gives the highest r2 correlation coefficient. High regeneration efficiency (more than 90%) over a number of cycles is obtained by passing a charge of 6.4 C g-1 of the GIC adsorbent, at a current density of 5 mA cm-2 using a batch, sequential adsorption (60 min) and electrochemical regeneration (30 min) process. The simultaneous adsorption and regeneration process indicates that 100 % AV 17 can be removed in 60 min (4L of 100 mg L-1 AV 17 solution, 140g of the GIC adsorbent, current density of 5mA cm-2). The flow behaviour in the electrochemical reactor has been studied using a pulse tracer technique. The residence time distribution shows that the flow behaviour in the liquid-spouted reactor can be regarded as a plug flow in series with a continuous stirred tank reactor. For the batch adsorption system, a “parallel adsorption barren well hypothesis” is proposed in this thesis. For the batch simultaneous adsorption and electrochemical regeneration system, a multi-parameter model is proposed in this thesis.

The study of acid rock and mine (ARD and AMD) environments mainly focused on the mineralogical and microbiological conditions and responses of such systems. Most of the research that involved some organic viewpoint was related to the amelioration of the environmental conditions, sometimes with contradictory results. How organic matter (OM) participates and which organic fractions are involved in ARD and AMD processes remain unclear. In this work we have applied organic geochemistry tools combined with mineralogical ad molecular microbiology techniques to study of ARD and AMD environments. The main objectives were to identify and characterise the natural sources of OM occurring both at ARD and AMD sites, and to determine whether the OM sources identified are involved in the generation or amelioration of AMD/ARD. This study shows that multiple OM sources occur naturally in acid drainage environments, included plant derived material and mature, petroleum-derived hydrocarbons, originating from the source rocks, apparently have not directly influence on the processes. This suggests that the generation of ARD and AMD is a completely chemoautotrophic process. Particle size of the iron phases present at ARD sites seems to be involved in the iron bioavailability. The presence of goethite in ARD/AMD systems may have a relationship with the presence of OM. Stimulation of ARD sediments using plant derived OM, abundantly present in and around ARD and AMD ponds systems does not result in the neutralisation of ARD or AMD. This suggests that plant material is not used by Fe(III)-reducing bacteria. However, it fuels fermentation processes and it is likely that fermentation products such as acetate, detected in microcosms and in situ, could limit Fe(III)-reduction. In contrast, the stimulation of ARD sediments using manure (particularly sheep manure) raises the pH up to near neutral conditions. Although it remains unclear which OM fraction from the manure is actively involved in the neutralisation of ARD; these results suggest that manure may make an interesting and non-expensive electron donor in AMD/ARD treatments.

An accurate model for RO process has significant importance in the simulation and optimization proposes. A steady state model of RO process is developed based on solution diffusion theory to describe the permeation through membrane and thin film approach is used to describe the concentration polarization. The model is validated against the operation data reported in the literature. For the sake of clear understanding of the interaction of feed temperature and salinity on the design and operation of RO based desalination systems, simultaneous optimization of design and operation of RO network is investigated based on two-stage RO superstructure via MINLP approach. Different cases with several feed concentrations and seasonal variation of seawater temperature are presented. Also, the possibility of flexible scheduling in terms of the number of membrane modules required in operation in high and low temperature seasons is investigated A simultaneous modelling and optimization method for RO system including boron removal is then presented. A superstructure of the RO network is developed based on double pass RO network (two-stage seawater pass and one-stage brackish water pass). The MINLP problem based on the superstructure is used to find out an optimal RO network which will minimize the total annualized cost while fulfilling a given boron content limit. The effect of pH on boron rejection is investigated at deferent seawater temperatures. The optimal operation policy of RO system is then studied in this work considering variations in freshwater demand and with changing seawater temperature throughout the day. A storage tank is added to the RO layout to provide additional operational flexibility and to ensure the availability of freshwater at all times. Two optimization problems are solved incorporating two seawater temperature profiles, representing summer and winter seasons. The possibility of flexible scheduling of cleaning and maintenance of membrane modules is investigated. Then, the optimal design and operation of RO process is studied in the presence of membrane fouling and including several operational variations such as variable seawater temperature. The cleaning schedule of single stage RO process is formulated as MINLP problem using spiral wound modules. NNs based correlation has been developed based on the actual fouling data which can be used for estimating the permeability decline factors. The correlation based on actual data to predict the annual seawater temperature profile is also incorporated in the model. The proposed optimization procedure identified simultaneously the optimal maintenance schedule of RO network including its design parameters and operating policy. The steady state model of RO process is used to study the sensitivity of different operating and design parameters on the plant performance. A non-linear optimization problem is formulated to minimize specific energy consumption at fixed product flow rate and quality while optimizing the design and operating parameters. Then the MINLP formulation is used to find the optimal designs of RO layout for brackish water desalination. A variable fouling profile along the membrane stages is introduced to see how the network design and operation of the RO system are to be adjusted Finally, a preliminary control strategy for RO process is developed based on PID control algorithm and a first order transfer function (presented in the Appendix).

Ce travail de thèse s’inscrit dans le cadre de la modélisation distribuée de la partition ruissellement-infiltration en milieu naturel. Notre démarche consiste à étudier la réponse de systèmes naturels complexes à partir de mesures locales, d’expérimentations numériques et de modèles distribuées. Les expériences de la parcelle de Thiès (40m2), au Sénégal, montrent que les hétérogénéités de rugosités mettent en défaut les lois de friction classiques (Manning, Darcy- Weisbach) des modèles de ruissellement qui sous estiment les hautes vitesses. Deux lois qui prennent en compte la hauteur de submersion de la rugosité de manière physique ou empirique sont testées. Dans le bassin versant de Houay Pano, les données obtenues sous pluie simulées, sur des placettes de 1m2, permettent de mettre en évidence l’effet des hétérogénéités, en particulier en terme d’encroutement du sol et de végétation, sur le ruissellement intégré spatialement. L’infiltration moyenne apparait comme dépendante de l’intensité de pluie et l’effet d’une distribution statistique d’infiltrabilité sur le transitoire et le permanent d’infiltration est étudié. La distribution exponentielle d’infiltrabilité semble la plus adaptée, elle est utilisée pour analyser la variabilité spatiale et temporelle de la production de ruissellement dans le bassin versant sous pluie naturelle. Enfin, ce modèle exponentiel, simple mais pertinent à l’échelle du mètre, est implémenté pour représenter un pixel de base dans un modèle de ruissellement-infiltration à l’échelle d’un sous bassin versant de 0.5 ha et différents scénarios de modélisation sont envisagés / This work deals with distributed modeling of runoff-infiltration processes in a natural environment. The response of complex natural systems is studied from local measurements, numerical investigations and distributed models. Experiments held in Thies, Senegal, on a 40m2 plot show that the heterogeneity of the surface put in the wrong classical friction laws (Manning, Darcy-Weisbach) of runoff models, because they underestimate high velocities. Two laws, taking physically or empirically into account the submersion of rugosity, are tested. In the Houay Pano catchment, we highlight from simulated rainfall experiments on 1m2 plots the effects of heterogeneities, mainly due to soil crusting and vegetation, on the spatially integrated runoff. We observed that the mean infiltration rate is dependent of the rainfall intensity and studied the effects of a statistical distribution of infiltrabilities on permanent and non-permanent infiltration. The exponential distribution of infiltrabilities appeared to be the best suited distribution. It is used to analyze spatial and temporal variability of runoff production in the catchment under natural rainfall, in order to obtain a per land use characterization of infiltration. Eventually, this simple but accurate model at the meter scale is implemented as a base pixel into a runoff-infiltration model at the sub-catchment scale (0.5 ha)

Substantial anthropogenic change of the Earth’s climate is modifying patterns of rainfall, river flow, glacial melt and groundwater recharge rates across the planet, undermining many of the stationarity assumptions upon which water resources infrastructure has been historically managed. This hydrological uncertainty is creating a potentially vast range of possible futures that could threaten the dependability of vital regional water supplies. This, combined with increased urbanisation and rapidly growing regional populations, is putting pressures on finite water resources. One of the greatest international challenges facing decision makers in the water industry is the increasing influences of these “deep” climate change and population growth uncertainties affecting the long-term balance of supply and demand and necessitating the need for adaptive action. Water companies and utilities worldwide are now under pressure to modernise their management frameworks and approaches to decision making in order to identify more sustainable and cost-effective water management adaptations that are reliable in the face of uncertainty. The aim of this thesis is to compare and contrast a range of existing Decision Making Methods (DMMs) for possible application to Water Resources Management (WRM) problems, critically analyse on real-life case studies their suitability for handling uncertainties relating to climate change and population growth and then use the knowledge generated this way to develop a new, resilience-based WRM planning methodology. This involves a critical evaluation of the advantages and disadvantages of a range of methods and metrics developed to improve on current engineering practice, to ultimately compile a list of suitable recommendations for a future framework for WRM adaptation planning under deep uncertainty. This thesis contributes to the growing vital research and literature in this area in several distinct ways. Firstly, it qualitatively reviews a range of DMMs for potential application to WRM adaptation problems using a set of developed criteria. Secondly, it quantitatively assesses two promising and contrasting DMMs on two suitable real-world case studies to compare highlighted aspects derived from the qualitative review and evaluate the adaptation outputs on a practical engineering level. Thirdly, it develops and reviews a range of new potential performance metrics that could be used to quantitatively define system resilience to help answer the water industries question of how best to build in more resilience in future water resource adaptation planning. This leads to the creation and testing of a novel resilience driven methodology for optimal water resource planning, combining optimal aspects derived from the quantitative case study work with the optimal metric derived from the resilience metric investigation. Ultimately, based on the results obtained, a list of suitable recommendations is compiled on how to improve the existing methodologies for future WRM planning under deep uncertainty. These recommendations include the incorporation of more complex simulation models into the planning process, utilisation of multi-objective optimisation algorithms, improved uncertainty characterisation and assessments, an explicit robustness examination and the incorporation of additional performance metrics to increase the clarity of the strategy assessment process.

Les outils actuels de gestion en temps réel des réseaux s’appuient sur deux outils logiciels : les logiciels de prévision météorologique et les logiciels de simulation hydraulique. L’usage des premiers est une cause importante d’imprécision et d’incertitude, l’usage des seconds oblige à des pas temporels de décision importants du fait de leur besoin en temps de calcul. Cette façon de procéder fait que les résultats obtenus sont généralement éloignés de ceux attendus. L’idée force du projet CARDIO est de changer de paradigme de base en abordant la problématique par la face « automatique » plutôt que par celle « hydrologie ». L’objectif est de rendre possible la réalisation d’un grand nombre de simulations en des temps très courts (quelques secondes) permettant de se passer des prévisions météorologiques en utilisant directement les données pluviométriques recueillies en temps réel. L’objectif est de parvenir à un système où la prise de décision est réalisée à partir de données fiables et où la correction de l’erreur est permanente. / Generally, real-time management of sewer systems uses two main tools. The first software one, dedicated to weather forecast is known by their imprecision and uncertainty. The main issue of the second one concerns their computational complexity, which becomes a burden, as they require temporal important steps of decision. This leads to an important problem, where the obtained results are generally different from the really waited ones. The main idea and objective of the CARDIO project, which are the core of this thesis, is to deal with this important problem using a new paradigm based on “automatic” concepts rather than applied from “hydrology” point of view. Such approach allows the realization of a large amount of numerical simulation in a fast way during a very short time (a few seconds). This allows dispensing of weather forecast by using real-time meditative pluviometric data directly. The objective is to achieve a system where the decision-making is made based on reliable data and also, the error correction is permanent.

The presence of subseismic scale faulting within high porosity sandstone reservoirs and aquifers represents a significant source of uncertainty for activities such as hydrocarbon production and the geologic sequestration of carbon dioxide. The inability to resolve geometrical properties of these smaller scale faults, such as size, connectivity and intensity, using conventional subsurface datasets (i.e. seismic reflection tomography, wireline log and core), leads to ambiguous representations within reservoir models and simulators. In addition, more fundamental questions still remain over the role of cataclastic faults in the trapping and transfer of mobile geofluids within the subsurface, particularly when two or more immiscible fluid phases are present, as is the case during hydrocarbon accumulation, waterflood operations and CO2 injection. By harnessing recent developments in 3D digital surface and volume imaging, this study addresses uncertainties pertaining to the geometrical and petrophysical properties of subseismic scale faults within porous sandstone reservoirs. A novel structural feature extraction and modelling framework is developed, which facilitates the restoration of fault and fracture architecture from digital rock surface models. This framework has been used to derive volumetric fault abundance and connectivity from a normal sense array of cataclastic shear bands developed within high porosity sandstones of the Vale of Eden Basin, UK. These spatially resolved measures of discontinuity abundance provide the basis for the geostatistical extrapolation of fracture/fault intensity into reservoir modelling grids, which promises the introduction of a much higher degree of geological realism into discrete fracture network models than can currently be achieved through purely stochastic methods. Moreover, by establishing spatial correspondences between volumetric faulting intensity and larger scale features of deformation observed at the study area (cataclastic shear zones), the work demonstrates the potential to relate reservoir equivalent measures of fault or fracture abundance obtained from outcrop to seismically resolvable structures within the subsurface, aiding the prediction of reservoir structure from oilfield datasets. In addition to the derivation of continuum scale properties of sub-seismic scale fault networks, a further investigation into the pore-scale controls which govern the transfer of fluids within cataclised sandstones has been conducted. Through X-ray tomographic imaging of experimental core flood (scCO2-brine primary drainage) through a cataclastic shear band bearing sandstone, insights into the influence that variations in fault structure exert over the intra-fault drainage pathway of an invading non-wetting fluid have been gained. Drainage across the fault occurs as a highly non-uniform and non-linear process, which calls into question the practice of using continuum methods to model cross fault flow. This work has also provided an improved understanding of the role that high capillary entry pressure cataclised regions play in modifying pore-fluid displacement processes within the surrounding matrix continuum. In particular, the high sweep efficiency and enhanced non-wetting phase pore-wall contact relating to elevated phase pressure observed during drainage points towards favourable conditions for wettability alteration within cataclised sandstones. This is likely to negatively impact upon the effectiveness of oil recovery and CO2 sequestration operations within equivalent reservoir and aquifer settings.

Gravel filters are potentially a low cost, low maintenance water treatment solution. They require no mechanical or electrical parts and can operate without the addition of chemicals or the need for close supervision. As such, they are an appropriate technology for treating road runoff as a component of Sustainable urban Drainage Systems (SuDS) and as an initial stage of drinking water treatment in rural areas. However, the processes by which pollutant particles are removed in gravel filters are poorly understood and practical experience shows that many filters fail long before their expected design life is reached. For this reason gravel filters are little used for drinking water treatment and, when they are incorporated into SuDS, their removal efficiency and maintenance requirements are unpredictable. The aim of this thesis was to better understand particle removal processes and the implications for gravel filter design. This was achieved through a combination of lab-based experiments and numerical modelling. • The change in conservative tracer transport characteristics with pollutant particle accumulation was assessed through column experiments. • The spatial heterogeneity of particle accumulation was measured by collecting 3D data with magnetic resonance imaging (MRI). Multiple scans of filters allowed the temporal evolution of particle accumulation to be assessed. A method for processing the raw MRI data to yield the change in 3D pore geometry was developed, assessed and applied. • A simple method for extracting and comparing pore network characteristics at different stages of particle accumulation was applied to the MRI derived geometry. • Direct modelling of the 3D MRI pore geometry with the open source software OpenFOAM allowed correlation of flow velocities with particle accumulation at each point in the pore network. Lagrangian particle tracking was used to simulate the transport of a conservative tracer through the filter. Key findings were that spatial heterogeneity in particle accumulation was influenced by both initial pore geometry and the temporal evolution of the pore network with accumulation. This was attributed to the formation of high velocity preferential flow paths that were evident in both the 3D MRI data and the numerical model of that data. Pore networks exhibited a decrease in connectivity with accumulation and this was mirrored by a decrease in the volume of the filter that was accessible to a conservative tracer. Conclusions of this thesis are that MRI is a useful tool for non-invasively assessing the spatial variability of clogging in gravel filters and, when combined with numerical modelling of the pore geometry, for establishing the link between pore velocity and particle removal. The formation of preferential flow paths is detrimental to the pollutant removal efficiency of a filter and could explain why many filters fail to produce good quality effluent well before their physical pollutant storage capacity is reached.

Over the last two decades, implementation of membrane bioreactors (MBRs) has increased due to their superior effluent quality and low plant footprint. However, they are still viewed as a high-cost option, both with regards to capital and operating expenditure (capex and opex). The present thesis extends the understanding of the impact of design and operational parameters of membrane bioreactors on energy demand, and ultimately whole life cost. A simple heuristic aeration model based on a general algorithm for flux vs. aeration shows the benefits of adjusting the membrane aeration intensity to the hydraulic load. It is experimentally demonstrated that a lower aeration demand is required for sustainable operation when comparing 10:30 to continuous aeration, with associated energy savings of up to 75%, without being penalised in terms of the fouling rate. The applicability of activated sludge modelling (ASM) to MBRs is verified on a community-scale MBR, resulting in accurate predictions of the dynamic nutrient profile. Lastly, a methodology is proposed to optimise the energy consumption by linking the biological model with empirical correlations for energy demand, taking into account of the impact of high MLSS concentrations on oxygen transfer. The determining factors for costing of MBRs differ significantly depending on the size of the plant. Operational cost reduction in small MBRs relies on process robustness with minimal manual intervention to suppress labour costs, while energy consumption, mainly for aeration, is the major contributor to opex for a large MBR. A cost sensitivity analysis shows that other main factors influencing the cost of a large MBR, both in terms of capex and opex, are membrane costs and replacement interval, future trends in energy prices, sustainable flux, and the average plant utilisation which depends on the amount of contingency built in to cope with changes in the feed flow.