Metal pollutants such as copper released into the aqueous environment have been increasing as a result of anthropogenic activities, a topic causing global concern. Adsorption-based treatment technologies offer opportunities to remediate metal pollutants from municipal and industrial wastewater effluent. The aim of this work was to evaluate the capability of modified cellulose nanowhisker (CNW) adsorbents for the remediation of copper from water matrices under realistic conditions using response surface methodology (RSM) and artificial neural network (ANN) models. The first part of the study explored the preparation and characterisation of modified CNW adsorbents. It also focused on the stability of the modified CNW adsorbents at different time intervals under dry conditions (up to 28 days) and in the water matrix (up to 7 days). The results showed that the modified CNW adsorbents were stable at different time intervals under dry conditions and in the water matrix and proved that the functional groups were permanent and did not degrade under the tested conditions. The stability of these modified CNW adsorbents under these conditions, which is relevant from both the manufacturing and application perspectives, is reported for the first time in this study. The second part of the work focused on using copper as a case study for heavy metal pollution in a clean water matrix, to evaluate removal by modified CNWs under several conditions and ranges appropriate to wastewater treatment plants (WWTPs), using factorial experimental design. RSM and ANN models were employed in order to optimise the system and to create a predictive model to evaluate the Cu(II) removal performance by the modified CNW adsorbents. Moreover, unseen experiments not belonging to the training data set, located both inside and outside the test parameter system, were performed to test the model suitability. This is also novel, as generally only one or two parameter variations have been tested, without checking the chosen model suitability for parameters lying between the tested parameters, and certainly not for parameters lying outside the tested parameter space, as has been done in this study. The results obtained showed that the ANN model outperformed the RSM model when predicting copper removal from a clean water matrix. The Langmuir andFreundlich isotherm models were applied to the equilibrium data, and the results revealed that the Langmuir isotherm (R2 = 0.9998) had better correlation than the Freundlich isotherm (R2 = 0.9461). Experimental data was also tested in terms of kinetics studies using pseudo-first order and pseudo-second order kinetic models. The results showed that the pseudo-second-order model accurately described the kinetics of adsorption. The third part of the work was aimed at gaining a deeper understanding of the complexity and variability of the wastewater matrix, including evaluating the impact of the wastewater matrix temporally on adsorbent performance to remediate copper pollutant from a real-world wastewater matrix. This study has demonstrated that the wastewater matrix composition, which is both complex and variable, has an impact on adsorbent capability and performance. A benchmark study was adopted as a ‘new’ water quality parameter to inform on the effects of the wastewater matrix (wastewater composition and its variability) on the modified CNW adsorbent’s capability to remediate copper from this matrix. Since the process of adsorption from wastewater is often complicated due to the variation in wastewater composition, results obtained from the benchmark experiments were included as one of the independent variables in ANN modelling, unlike in other optimisation studies. The performance of the ANN and RSM models was statistically evaluated in terms of coefficient of determination (R2), absolute average deviation (AAD), and root mean squared error (RMSE) on predicted experimental outcomes. The ANN model including the variability of wastewater composition fitted the experimental data with excellent accuracy and better prediction (R2 = 0.9963) than both the ANN model that did not include this variability (R2 = 0.9945), and the RSM model (R2 = 0.9409). The outcome of this study showed that by supplying the ANN model with the data obtained from the benchmark experiments as the fourth independent variable, it was possible to improve the predictability of the ANN model. Continuous flow experiments for remediation of spiked Cu(II) from the wastewater matrix were conducted. However, the physical structure of modified CNW adsorbents renders them unsuitable for use in column operation. Therefore, a more detailed study of the mechanical properties of CNW adsorbents would be necessary in order to improve the strength and stability of the adsorbents. This work has demonstrated that modified CNW are promising adsorbents to remediate copper from water matrices under realistic conditions including wastewater complexity and variability. The use of models to predict the test parameter system and account for matrix variability when evaluating CNW adsorbents for remediating Cu from a real-world wastewater matrix may also provide the foundation for assessing other treatment technologies in the future.

Membrane filtration and Advanced Oxidative Processes (AOPs) are among the most efficient and cost-effective methods employed in water purification. A system to integrate the two methods using photoactive colloidal particles was studied in this thesis, with the final purpose of overcoming membrane fouling, one of the main issues occurring in filtration processes. The production of nanostructured TiO2 microparticles through a simple and extremely rapid synthesis and an easy method to assemble a multifunctional coating, integrating inorganic particles on filtration membranes, were targeted as the most promising solutions from the technological and environmental point of view. The control of microwave-assisted heating applied to hydrothermal treatments, a relatively recent synthetic method, allowed the production of nanostructured mesoporous spherical TiO2 particles, bringing the synthesis to the minute scale, extremely rapid compared with conventional heating, and achieving products otherwise difficult to obtain without the help of surfactants or templating agent. The as-synthesised particles showed photoactivity under visible light, with rate of specific reactions (selective de-ethylation) 4 times higher compared with commercial photocatalysts. Furthermore, the particles were modified to extend the limited intrinsic absorbance of TiO2 in the visible light, with promising results given by formation of stoichiometric defects (in particular oxygen vacancies) through annealing under vacuum. This treatment allowed the achievement of comparable or even higher performance in photocatalytic degradation of rhodamine B with respect to commercial TiO2 photocatalysts, including Aeroxide P25, with degradation rate towards organic molecules (rhodamine B) of even 60-70% after 1 hours, compared to the 25% of P25. The production of a multifunctional coating for water treatment by integration of colloidal and nanometric TiO2 particles has been also studied. A simple technique to integrate TiO2 nanoparticles onto different substrate, in particular filtration membranes, was developed by simple electrostatic interactions involving the use of polyelectrolytes, water-soluble charged polymer forming organised layers when assembled in a macromolecular structure defined as polyelectrolyte multilayers (PEMs). Electrostatic assembly was applied as an environmentally friendly technique to anchor nanoparticles (P25) on different surfaces, transferring their properties to these. In particular, the application of TiO2 particles conferred hydrophilic and superhydrophilic to a relatively hydrophobic surface (Mylar) by controlling the multilayer assembly conditions, in particular the ionic strength of the polyelectrolyte solutions. The achievement of superhydrophilic behaviour on the treated surfaces, with contact angles below 15° on Mylar surfaces, and the possibility of removing fouled active layer from a membrane replacing it with a newly generated one can be both implemented as potential antifouling strategies in water treatment.

The hydrodynamic vortex separator (HDVS) is currently employed at wastewater treatment works and in the sewerage system as a combined sewer overflow (CSO) for the separation of solids from an incoming waste stream. This project presents the first stage in developing and aiding the existing design methodology for the optimisation of kinetic processes within the HDVS. The kinetic process design methodology combines hydraulic and kinetic principles by using the true mixing regime characteristics of a system and batch reactor data to determine a kinetic processes efficiency. This project used residence time distribution (RTD) analysis to extensively characterise the mixing regime within a model and prototype HDVS. The HDVS was operated with and without a baseflow component and with and without the sludge hopper for a range of inlet flow rates and flow splits covering design flow rates for a number of existing applications. The RTD was obtained using a pulse tracer injection method and described using the complete range of data analysis techniques typical employed in RTD studies. This includes the axial dispersion model (ADM), tanks-in-series model (TISM), RTD indices and a RTD combined mathematical model. The combined model is configured to quantify the inactive flow behaviour within the HDVS i. e. stagnant and dead volumes. The HDVS has a complex imperfect plug-flow mixing regime. This non-ideal flow behaviour is associated with both dispersion and dead volumes and results in short-circuiting. At low flow rates the HDVS operating without a baseflow contains fluid elements which conduct flow slower than the mean velocity. At high flow rates the inactive flow behaviour is associated with dead volumes and subsequently short-circuiting. The flow rate at which this change in mixing characteristics occurs is termed the transition flow rate and is approximately 151/min and 901/min for the model and prototype HDVS respectively. At all flow rates above the transition flow rate the HDVS has a very stable mixing regime, which is associated with both the inactive flow behaviour and the plug-flow mixing characteristics. The ADM and TISM parameters increase as the flow rate decreases and therefore, the HDVS has improved plug-flow mixing characteristics and reduced dispersion at low flow rates. Removing the sludge hopper reduces the inactive flow behaviour and improves the plug-flow mixing characteristics. The inactive flow behaviour within the model HDVS operating with no baseflow occupies approximately 20-40% of the total volume and similarly for the prototype HDVS 5-25% and increases as the inlet flow rate increases. The inactive flow behaviour occupies a smaller fraction of the total volume and the plug-flow mixing characteristics are also improved as the HDVS is scaled-up in size. Hence, the scale-up of the HDVS will provide a mixing regime with less short-circuiting and improved plug-flow mixing characteristics and therefore, more conducive for certain kinetic processes and particularly chemical disinfection processes. The introduction of a baseflow component alters the total mixing regime within the HDVS. The baseflow component introduces an element of plug-flow mixing and subsequently the total plug-flow mixing characteristics of the HDVS operating with a baseflow component are greater than the HDVS operating without a baseflow. The baseflow component plug-flow mixing characteristics increase and the overflowcomponent decrease as the inlet flow rate increases. Short-circuiting of the baseflow and overflow component occurs as the inlet flow rate decreasesa nd increasesr espectively. Hence, there are different mixing regimes within the HDVS associated with the overflow and baseflow component. The HDVS operating with a baseflow component has improved plug-flow mixing characteristics when the sludge hopper is included. This project was also extended to include an experimental kinetic process analysis, by investigating the first-order decomposition of hydrogen peroxide (H202) using catalase. This was undertaken to compare the actual kinetic process performance within the HDVS to that estimated using the RTD. The H202 decomposition results showed that the design of the HDVS for kinetic processes can be achieved using only the RTD and relevant batch reactor data. This enables the HDVS to be optimised for kinetic process applications and eliminates the need for costly and time consuming pilot trials. The characterisation of the HDVS using RTD analysis creates scope for significant future research. This includes: alternative experimental RTD techniques, development of the RTD combined mathematical model to include a baseflow component and kinetic process principles, extensive kinetic process batch reactor investigations, application of both the hydraulic and kinetic data into chemical reactor design computer software and finally the scaling of the HDVS using the RTD and therefore the kinetic process optimisation. This work is a proactive response by practitioners and Hydro International Plc to pressure from the regulators and EU Directives, placing emphasis on the use of sophisticated treatment processes based on good scientific principles, to meet current and future stringent water quality standards.

In the UK, the Water Services Regulation Authority (OFWAT), estimates that for all the water and sewage companies there was over 3,365 Ml/d (megalitres per day) of water leakage in the reported period 2010 and 2011, which was still at 3094.21 Ml/day in the 2013 review. Leakage estimates do not include water siphoned illegally through unaccounted connections worsened as asset management of buried utility services has been overlooked for years. With the asset management programme framework (AMP6) due to come into effect in April 2015, water companies are expected to get more out of their existing infrastructure and making considerable investment while keeping bills reasonable for customers. Improving the management of these assets is therefore a priority, as effective asset management enables companies to reduce cost, through leakage management, to plan investments and repairs, and to evaluate operational risks by better fault prediction rather than the current reactive approach. This research focuses on the water distribution network as an asset that include leaks and pipe infrastructure with different materials and diameters. A novel method for leak detection and asset management using an electromagnetic sensor has been developed. Trials in the laboratory showed the sensor is capable of detecting pipe types and conditions thus improving leak detection and asset management in the water industry without extensive digs and modification to existing access valves within the network for system deployment. Furthermore, the sensor would potentially benefit the gas industry by modifying the frequency of operation to match gas filled cylindrical metal structures.

This research aims to propose an integrated method, which combines all the aspects required to reduce environmental impact from waste packaging and to increase knowledge on the best way to enhance reusable packaging. Through a review of the extant literature, a conceptual framework was designed of the most important dimensions to enhance reusable packaging amongst society and industries The main contributions in the research are the development of a Social Behaviour Aspect Model (SBAM) and the creation of reusable packaging attributes checklist. The SBAM can help industries focus on having high knowledge about reuse of packaging and to cooperate with communities to develop personal and social values and norms during the designing of reusable packaging. SBAM is the output from the first phase, which showed the importance of making an effort to develop packaging for consumers to reuse. The reusable packaging attributes checklist can provide a guideline for manufacturers/designers who intend to develop packaging sustainability performance through designing reusable packaging, and contribute to meet and interpret the reuse of packaging requirements and procedures. It also determines the environmental impact of reusable packaging attributes, which many industries are concerned about. The reusable packaging attributes checklist is the output from the second and third phases. The System Dynamic (SD) method was the approach used to determinate the interaction between social aspects and reusable packaging. The Normal Average, Codes and Coding and factor analysis with Principal Component Analysis (PCA) approaches were used to determine the reusable packaging attributes checklist. The last phase of the research was the conduction of a case study of a real company which needs to increase the amount of reusable packaging it uses and which seeks to reduce its environmental impact. All methods used in this research have both a quantitative and a qualitative nature. Data was collected by evaluation of consumers' responses and experts' experiences, as provided in the questionnaires. This research opens up opportunities for improving packaging and meeting sustainable profits and provides valuable information based on social, economic and environmental benefits of reusable packaging. The novelty of this research can help industries to investigate the most important areas for development within communities to enhance the use of reusable packaging and also facilitate the process-based change from one-way packaging to reusable packaging effectively with reduction of environmental impact.

Orientador: Antonio Luiz Caldas Júnior / Banca: Carlos MagnoCastelo Branco Fortaleza / Banca: Francisco Antonio de Castro Lacaz / Resumo: A construção do SUS, ao longo de décadas recentes, tem sido espaço de relevantes conquistas, a despeito de conflitos e dificuldades. Observa-se, porém, que a municipalização da vigilância sanitária (Visa) não acompanhou o ritmo e a intensidade geral do processo. O presente estudo discute e analisa os aspectos da municipalização das ações de vigilância sanitária, na percepção de seus gestores, com ênfase no desenvolvimento deste processo no município e seus determinantes políticos, técnicos e administrativos. O cenário da pesquisa foi composto por cinco municípios do interior do Estado de São Paulo, na área de abrangência da então Direção Regional de Saúde de Botucatu, em gestão plena do sistema de saúde. As informações foram colhidas por meio de entrevistas semi-estruturadas e trabalhadas em abordagem qualitativa buscando a construção de categorias e unidades discursivas explicativas do processo estudado. Ao final, aponta que, na visão dos gestores municipais, se evidenciaram vários conflitos. Verificou-se o comprometimento do desenvolvimento das ações de vigilância sanitária diante da figura da "ingerência política" de prefeitos, vice-prefeitos e vereadores que priorizam interesses individuais do setor regulado em detrimento de normas sanitárias. Outro aspecto destacado foi a posição secundária atribuída às vigilâncias na estrutura e nas prioridades da saúde municipal, explicitando por que o processo de municipalização de suas ações não transcorreu na mesma velocidade e profundidade das ações assistenciais. Constataram-se equipes de vigilância sanitária desmotivadas, com baixa qualificação, com rotatividade dos componentes, cingidas pelo estigma do setor como área de trabalho permeada por relações conflituosas. / Abstract: SUS creation has been achieving considering progress along decades, despite conflicts and difficulties. It has been observed, however, that the municipal sanitary surveillance (VISA) was not able to follow the rate and the general intensity of the process. The present study discusses and analyzes the municipal aspects of VISA, in its managers' perception, emphasizing this process development in the municipal district and its political determinants, technicians and managers. The research scenery was composed of five municipal districts in São Paulo countryside, in the Botucatu Regional Health Department, in full management of the health system. The information was collected through semi-structured interviews and developed in qualitative approach aiming at the category creation and explanatory discursive units of the studied process. At the end of this process, several conflicts were identified by the municipal managers. It was observed the compromising development of the sanitary surveillance in the presence of mayor', vice-mayor' and councilor's political intervention who prioritize individual interests of the regulated sections rather than the sanitary norms. Another aspect was the secondary position attributed to the surveillances in the structure and to the municipal health priorities, explaining the reason the municipal process of its actions was not developed with the same speed and depth of the social services. Discouraged groups of sanitary surveillance, with low qualification, with rotation of the components, surrounded by the stigma of the section as work area permeated by conflicting relationships were observed. It has also been demonstrated that the municipal managers of the area don't have the control of the financial resources available for sanitary surveillance, originated from agreements and adjustment terms of objectives. / Mestre

Recently, there has been an increased concern of the potential effects of pharmaceuticals, personal care products (PPCPs) and endocrine disrupting compounds (EDCs) in drinking water. Their presence in surface waters has resulted in the skewing of sex ratios in aquatic biota and the effect on humans, as yet, remains unknown. Investigation into the effective removal of these compounds by water treatment plants (WTPs) has shown that conventional treatment processes are not very effective in removing these trace compounds. Studies have shown PPCPs and EDCs have been successfully removed by commercial nanofiltration (NF) and reverse osmosis (RO) membranes, but have low flux and high cost. North American WTPs, using membrane separation processes, are typically equipped with microfiltration (MF) or loose ultrafiltration (UF) membranes which, thus far, have proven ineffective for the removal of these target compounds. This thesis focuses on the development of a tight charged UF membrane that effectively removes PPCPs and EDCs from drinking water while still maintaining a high flux and is cost effective. Novel membranes were developed by incorporating charged surface modifying macromolecules (CSMMs) in the manufacturing of polyether sulfone (PES) based membranes. The charged additives were expected to enhance the removal of PPCPs and EDCs by charge repulsion. Controls and three different CSMM (DEG-HBS, DEG-HBC and PPG-HBC) blended membranes were prepared at three different casting conditions and subsequently evaluated for various properties: flux, molecular weight cut-off (MWCO), porosity, charge and contact angle. Experimental membranes were further evaluated for the removal of four representative target compounds, sulfamethazine (SMZ), carbamazepine (Carb), bisphenol A (BPA) and ibuprofen (IB). Removal by a commercial nanofiltration membrane, NF270 (DOW/FilmTec) was compared to the experimental membranes. Removal results from the experimental membranes indicate membranes were unable to sustain effective removal of the target compounds. Typically, removal was initially high but decreased over the run. Membrane characteristics showed membranes had significantly larger pores than the target compounds indicating size exclusion was not the removal mechanism. Charge results indicated CSMM blended membranes were generally unchanged from the control membrane indicating, in addition to the unsustained removal, that charge repulsion was not the removal mechanism. From the shape of the removal curves, it is assumed the removal mechanism is the result of membrane adsorption. The CSMMs were found to have modified the membranes, though not sufficiently, to be considered significantly different than the controls in many respects. Membrane characteristics varied as a result of each CSMM incorporated and depending on each casting condition. Contact angle results for both PES-DEG-HBS and PES-PPG-HBC membranes at all three casting conditions increased in comparison to the controls, presumably because of changes in surface roughness. PES-DEG-HBC, on the other hand, decreased in contact angle at 18%, and increased in contact angle at 20% in comparison to the respective controls. Incorporation of migration time, particularly in the case of DEG-HBC, increased membrane flux without affecting MWCO. Increased PES concentration (from 18 to 20%) saw an increased target compound removal. With the success of the DEG-HBC CSMM, incorporation of migration time at higher PES concentrations appears promising for achieving the desired characteristics. It is recommended that further optimization using CSMM DEG-HBC at increased PES concentrations with migration time be investigated for this application.

In September 2005, Health Canada took on the development of a Source Water Quality Indicator for Canada. The main objective was to develop a methodology by which source water quality could be linked to public health, the environment, society, and economy; and measured, tracked, and reported in the form of an indicator for decision making. A Treated Water Quality Indicator was also introduced to bridge the gap between source water quality and human health. With Federal/Provincial/Territorial and academic support, research into the approach and development of a conceptual design, parameter selection rationale, and two tools for the indicator calculations, along with recommendations for future work were completed. The tools developed included a modified Canadian Council of Ministers of the Environment water quality index calculator, and a Treatability Ranking tool (that determined the complexity of treatment required to achieve safe drinking water). The results of this project are described herein.

The efficacy of pond treatment systems is dependent on the internal hydrodynamic and mixing interactions between aquatic vegetation and the adjacent flow. In attempting to improve pollution degradation and reduce the effects of hydraulic short circuiting, an understanding and quantification of these interactions was sought for seasonal changes in vegetation growth. Controlled laboratory studies were conducted using detailed Laser Induced Fluorometry (LIF) and Ultrasound Velocity Profiling (UVP) techniques to quantify mixing across vegetated shear layer, emergent Cattail reeds (Typha latifolia). An Optimised Finite Difference Model (OFDM) was developed to predict the best fit downstream concentration distributions given the input profiles of transverse mixing coefficient, Dy(y). The model provided strong fitting in artificial vegetation (R2 = 0.977 and 0.969 for high and low density rigid cylinders). A good fitting was also made for the winter reeds (R2 = 0.976); although the physical application of conventional shear layer theory failed to significantly improve predictions in the summer season reeds above those of a simple discontinuity functionality describing Dy(y). The form of the lateral variation in transverse mixing coefficient was confirmed in the artificial vegetation studies where peak mixing is enhanced by shear layer vortices. However, in real vegetated shear flows, the heterogeneities in stem morphology and distribution render the relative magnitude of shear layer mixing diminished when compared to other regions of the flow. It is shown that, while the OFDM provides good predictions of concentration distributions when using a physically justified profile of the transverse mixing coefficient, a discrete step formulation is sufficient for describing mixing in real vegetated shear flows. This study shows therefore, that, while shear layer mixing is dominant in artificial, uniform vegetation, transverse mixing in real vegetated flows is dominated by complex geometries, localised shear processes and bed roughness effects.

The Nigerian economy has relied heavily on crude oil production since independence in 1960. As a consequence, it has seen an influx of multinational petroleum companies with oil exploration and associated activities having significant environmental impacts, particularly oil leakage and spillage into soil and the overall degradation of the ecosystem in the Niger Delta area. This study aims to find a viable solution to the remediation of polluted soil by comparing two thermal remediation techniques, namely microwave pyrolysis and traditional pyrolysis, which has been investigated using a Gray-King retort. The polluted soil was first examined to ascertain the distribution of the soil organic carbon (SOC) with 78% found to be solvent extractable in dichloromethane/methanol, while 95 % was thermally labile and removed under hydropyrolysis (HyPy) conditions at 550 °C. The remaining 5 % of the SOC was composed of a recalcitrant residue being defined as the black or stable polyaromatic carbon fraction. The solvent extractable organic matter (EOM) was then further separated into the maltene (free phase) and asphaltene (bound phase) fractions together for comparison with a sample of Nigerian crude oil provided by the Shell Petroleum Development Company (SPDC), Nigeria. The Nigerian crude oil is a light crude oil with the percentage of maltene (95.2 %) was far higher than the asphaltene (4.8 %). A closer margin was observed in the percentage between the maltene (88.3 %) and asphaltene (11.7 %) in the soil EOM due to biodegradation. The biomarker profile of the EOM was compared with that of a Nigerian crude oil to confirm that the EOM contains the crude oil in the soil. Their biomarker profiles revealed that the source inputs were terrigenous from deltaic settings, of Late Upper Cretaceous age and deposited under oxic conditions. Oleanane (a pentacyclic triterpene, abundant in oils from the Niger Delta) was present in both the crude oil and EOM and the hopane and the sterane distributions (m/z 191 and m/z 217 respectively) were similar in every respect, which indicates that the probable source of the pollutant crude oil in the soil is similar in composition to the Nigerian crude oil. Accordingly, the polluted soil was treated with microwave pyrolysis and Gray-King pyrolysis to remove the crude oil pollutant. The maximum average recovered products from the thermal remediation process with Gray-King pyrolysis is 99.4 % TOC and maximum crude oil pollutant removed by Gray-King pyrolysis was 85.3 % TOC with maximum oil recovery of 70 % TOC from all the different treatment conditions, while the shortest treatment time condition gave the lowest gas yield of 10.2 % TOC. This implies that 100 % removal with respect to EOM and 89 % removal with respect to HyPy as discussed above. Furthermore, the polluted soil was also treated with microwave pyrolysis with maximum pollutant removal of 77 % TOC, which is 98.7 % removal with respect to EOM and 81 % with respect to HyPy. In conclusion, Gray-King pyrolysis removed more of the soil organic carbon than microwave pyrolysis, but the latter does have advantages regarding operability and greater output within a short treatment time.