Monitoring for pollutants in potable water is an area of interest and concern for water supply companies. Supply of sub-standard water can draw complaints from public and industrial customers. Water and water tainted with pollutants were used to assess the application of a non-specific chemical sensor array (eNose) to monitor for changes in the headspace generated from a flow-cell by means of statistically designed experiments. 2-chlorophenol and diesel were used to further assess trends in headspace generation during trials where different combinations of sampling parameters were applied. Field trials were conducted in accordance with the most suitable methodology determined during initial studies under laboratory conditions. The headspace is generated by bubbling nitrogen through the flow-cell containing a water sample. The liquid sample is flushed and regenerated after each sensor acquisition cycle. The resultant headspace sample is transferred to the sensor array module where the resistance of the conducting polymer sensors is monitored as they are exposed to each respective headspace sample. The change in each sensor resistance after 60 seconds of exposure is used to represent the headspace character. Subsequent acquisitions are added to a data set and then presented graphically. Sudden changes in the sensor resistance plots represent changes in water quality. The results showed that the developed apparatus and sampling methodology can determine the presence or absence of pollution in a water matrix. Laboratory analysis showed that detection levels for 2-chlorophenol and diesel were both <5 ppm in the mixed stream. Future developments should focus on increasing the sensitivity of the system by concentrating the pollutants in either the liquid or gas phase or by modifying the sampling protocol to enable sensor recognition at lower concentration levels. The sensor array could act as a screening technique to support quantitative and characterising analytical equipment at the abstraction point. Establishing a pollution alarm limit, within the bounds of acceptable system variation, would enable conventional analytical techniques to remain on standby until activated by a statistically significant change in water quality. Once established continued testing would enable alarm levels to be incorporated into a contaminant database for additional pollutant compounds and combinations of known taste and odour causing compounds.

No description available.

The production of both fresh water and waste streams are progressively increasing over the years due to ongoing population growth coupled with high levels of increase in water consumption. The ongoing growth of human activities, such as industry, recreation, and agriculture, are significantly contributing to the increase in both water demand and severity of degradation of natural water resources. The majority of the industrial wastewaters have a significant impact on the environment; some of which may pose a number of threats to human health and the surrounding environment. Thus, discharge of such waste streams into a surface water and/or groundwater presents a major source of water pollution in many countries. Therefore, these waste streams must be disposed of in an environmentally acceptable manner. The primary concern of the PhD thesis is to seek the most feasible and applicable freezing desalination technologies that are potentially capable to concentrate the dissolved ionic content of the liquid streams, especially for those causing severe pollution problems. Therefore, various forms of melt crystallisation processes, namely; agitated and static crystallisation processes, ice maker machines, a Sulzer falling film crystallisation process, the Sulzer suspension crystallisation process, and the Sulzer static crystallisation process, were experimentally used and investigated. The experimental investigations were carried out on the laboratory bench scale and/or straightforward pilot plant by using aqueous solutions of sodium chloride and/or process brines as feed samples. The study was focused on a number of important parameters influencing the separation performance of the investigated treatment systems. In general, the resulting experimental data for each innovative process were highly encouraging in minimising the volume of the waste stream, and substantially increasing the amount of product water. The obtained product water was ready for immediate use either as drinking water or as a saline water of near brackish water or seawater qualities. Also, relationships between the influences and the separation performance, in terms of salt rejection and water recovery ratios, were explored and determined for the investigated technologies. Based on the experimental results, the Sulzer melt crystallisation processes were scaled up and were combined into a commercial reverse osmosis membrane desalination plant. As a result, three novel treatment option configurations were proposed for minimising the waste stream, whilst increasing the production rate of drinking water and/or preserving a substantial amount of natural water resource from the RO plant's exploitation.

With ever increasing regulation of the quality of drinking water and wastewater treatment, there is a need to develop methods to remove nitrogenous compounds from water. These processes are mediated by a variety of micro-organisms that can oxidise ammonia to nitrate, and then reduced to gaseous nitrogen by another set of organisms. This two stage process involves the relatively slow oxidation of ammonia to nitrate followed a relatively fast reduction of nitrate to nitrogen. Nitrate reduction normally requires anaerobic environments and the addition of organic matter to provide reducing power (electrons) for nitrate reduction. In practical situations the nitrate reduction can be problematic in those precise quantities of organic matter to ensure that the process occurs while not leaving residual organic matter. The aim of this study was to investigate microbial denitrification using electrochemical sources to replace organic matter as a redactant. The work also involved developing a system that could be optimised for nitrate removal in applied situations such as water processing in fish farming or drinking water, where high nitrate levels represent a potential health problem. Consequently, the study examined a range of developments for the removal of nitrate from water based on the development of electrochemical biotransformation systems for nitrate removal. This also offers considerable scope for the potential application of these systems in broader bio-nanotechnology based processes (particularly in bioremediation). The first stage of the study was to investigate the complex interactions between medium parameters and their effects on the bacterial growth rates. The results proved that acetate is a good carbon source for bacterial growth, and therefore it was used as an organic substrate for the biological process. High nitrate removal rate of almost 87% was successfully achieved by using a microbial fuel cell (MFC) enriched with soil inocula with the cathodes cells fed with nitrate and the anode fed with acetate. The maximum power density obtained was 1.26 mW/m2 at a current density of 10.23 mA/m2. The effects of acetate, nitrate and external resistance on current generation and denitrification activity were investigated, and the results demonstrated that nitrate removal was greatly dependent on the magnitude of current production within the MFC. Increase of acetate (anode) and nitrate (cathode) concentrations improved the process, while increasing external resistance reduced the activity. Furthermore, for a clear understanding of the nitrate reduction process, the analysis of the associated bacteria was performed through biochemical tests and examination of morphological characteristics. A diversity of nitrate reducing bacteria was observed; however a few were able to deliver complete denitrification. Pure cultures in MFC were examined and the voltage output achieved was about 36% of that obtained by mixed cultures. The nitrate removal gained was 56.2%, and this is almost 31% lower than that obtained by the mixed bacterial experiment. In an attempt to improve the MFC, modifications to the electrochemical properties of the electrode were investigated through the use of a cyclic voltammetry using carbon nanomaterials to coat the graphite felts electrodes. Among all the nanomaterials used in this study, graphitised carbon nanofibres (GCNFs) was selected for further investigation as it offered the best electrochemical performance and was thought to provide the largest active surface area. The performance of the MFC system coupled with the GCNFs modified electrodes was evaluated and significant improvements were observed. The highest voltage output achieved was about 41 mV with over 95% nitrate removal. The work is discussed in the context of improved MFC performance, potential analytic applications and further innovations using a bio-nanotechnology approach to analyse cell-electrode interactions.

An activated unsaturated sand filter (AUSF) is one of only a few of the filtration technologies utilized to treat waters and wastewaters that use unsaturated filter media. AUSF employs sand coated with potassium permanganate and operates with an open chamber allowing free air flow into the column of sand. The AUSF also benefits from operation without the need for a sedimentation unit. Previous studies have demonstrated the efficient removal of iron and manganese using an AUSF, however, to date there are still very limited studies available that use AUSF technology for the removal of metals from waters and wastewaters. Thus, there is an urgent need and opportunity to exploit this technology further. This research was conducted in order to develop and study the characteristics and subsequent operational performance of a novel AUSF media. The study focuses on the removal of copper, manganese, zinc and nickel from a synthetic wastewater and extends current knowledge to a passive aeration process rather than the active aeration used in the previous study by Lee et. al. (2004). The characterisation involved the use of sieving, Brunauer- Fmmett-Teller (BET) analysis, water evaporation studies and scanning electron microscopy (SEM) for structural analysis such as particle size, surface area, porosity and topography. Energy dispersive X-ray analysis (EDX), acid/alkali resistance, isoelectric point determination and acid digestion analysis were used to determine the chemical constituency, chemical stability, electrical charge properties and the binding efficiency of the media. Finally, tracer studies were employed to determine the flow characteristics through the particle media. The manganese coated sand was proven effective for the removal of copper in both agitated tank batch studies and continuous column studies. The batch studies showed that the equilibrium sorption of copper followed a Langmuir isotherm and the sorption rate was best modelled using the pseudo-second-order kinetic model. This suggests that adsorption is taking place as a single homogeneous layer on the surface of the sand particle via the chemisorption method. The Weber-Morris and Bangham models were used to determine the rate-controlling mechanism and this was found to be predominantly intra-particle diffusion. This was confirmed for column studies using the Bohart-Adams model that demonstrated that liquid-film mass transfer was not significant. Several mechanisms of metal removal are proposed and these include precipitation, electrostatic attraction, adsorption, ion exchange and complex ion formation. The column studies demonstrated that dispersion was low under the operating conditions and plug flow performance could be inferred, thus justifying the use of the AUSF model employed. Copper was best removed when operating as an unsaturated particle bed and the removal capacity was increased by approximately 100% when compared to a saturated particle bed. Moreover, the pH increase that occurs on exposure of the process water to the unsaturated column further improves removal capacity. Thus, there is no requirement for an expensive pH adjustment as a pre-treatment process prior to this unit operation. In addition, the removal capacity of the AUSF was demonstrated to increase with lower metal concentrations, lower water flow rates, smaller sand particles, an increase in manganese to sand ratio and an increase in particle bed height. The AUSF performance in removing metals followed the order Cu > Mn > Zn > Ni for individual and mixed component solutions and Cu > Ni > Zn > Mn for a synthetic wastewater typical of the electroplating industries. In conclusion, the novel manganese coated AUSF developed is effective in the removal of metals from solution and offers the potential of a sustainable low cost treatment method for the purification of waters and wastewaters.

Each and every one of us is exposed to chemicals on a daily basis and contributes to the global issue of chemical pollution. Humankind has become heavily dependent on the use of man-made chemicals in order to sustain the increased quality of life that is generally seen globally. There is however a price to pay in that we generally live in a world that is polluted by anthropogenic chemicals. From the water we drink to the food we eat there will be some trace of chemical residues; you just need to look closely enough and/or know what you’re looking for. With many hundreds of thousands of man-made chemicals approved within Europe for use in various ways, it is no surprise that we come into daily contact with them. What is also important to understand is that the presence of a man-made chemical is not enough to establish whether it poses a risk to environmental or human health; it needs to be present in sufficient amounts to elicit an effect. Over the past 20 years the focus of my research been on understanding which chemicals we should be concerned with, which pose the greatest risk and why do they pose such a risk. This work is of major societal and scientific significance as it protects the world we live in whilst teaching us about the better regulation of the chemicals we have become so dependent. To understand the nature of my research it is important to understand that prior to the mid-nineteen nineties hazardous organic chemicals were typically restricted to lists comprising of a number of banned (and typically chlorinated) pesticides, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans and the antifouling biocide tributyltin (TBT). One of the major enigmas that faced environmental scientists at the time was that even though it was possible to quantify and monitor the presence of the above hazardous substances in the environment, they often didn´t explain the environmental quality measured though biological effects on organisms. Chemicals are globally regulated on an individual substance level and subsequently within the context of influencing these regulations, for the improved protection of environmental and human health, it is therefore essential to know which chemical contaminants are actually causing biological effects. It is also necessary to know the levels at which any organism will be exposed and what the consequences of these levels. My research subsequently became focused on two separate approaches; identifying which substances actually cause the biological effects unexplained by hazardous substances and evaluating the occurrence, environmental fate and ecotoxicity of those chemicals not routinely monitored or present on priority lists of hazardous substances; a group of chemical contaminants later termed contaminants of emerging concern (CECs). An effect-directed non-target approach A targeted approach to environmental analysis infers that we know exactly what we should be looking for. Whilst this is a suitable approach for chemicals that we suspect may be of concern, it does not help us understand which other contaminants may be present in the environment and potentially causing harm. When embryos of oysters exposed to estuarine surface waters developed deformities and this could not be attributable to the levels of priority hazardous substances a bioassay-directed non-target approach to environmental analysis was developed to identify chlorinated and alkylphenols as responsible [5, 6]. This approach has subsequently evolved into the approach termed effect-directed analysis (EDA) and is widely used globally for the identification of CECs. My own research has successfully applied the approach to identify for the first time a number of important environmental contaminants; steroidal androgens [10, 13, 14] as environmental contaminants, the phthalate ester bis(2-ethylhexyl)phthalate [10], cinnarizine, cholesta-4,6.dien-3-one [19], C1-C5 and C9 alkylphenols [21], petrogenic naphthenic acids [57] as environmental estrogen receptor agonists, C1-C5 and C9 alkylphenols [21], PAHs and petrogenic naphthenic acids [57] as androgen receptor antagonists and unresolved polar aromatic compounds as important environmental genotoxins [15]. Another focus of my effects-directed research has been identifying environmental contaminants that exert the same effects as dibenzo-p-dioxins and polychlorinated dibenzofurans in that they are aryl hydrocarbon receptor (AhR) agonists. Dioxin-like chemicals are ubiquitous in the environment and in addition to those that are routinely monitored there are a large number of other compounds that exert dioxin-like effects [26, 28, 32, 33, 37, 52, 64, 82, 93, 98, 99]. Better understanding of AhR agonists will in the long run help protect the environment and humans from a particularly hazardous group of chemicals. A targeted approach The early- to mid-nineteen nineties saw the widespread introduction of liquid chromatography coupled to mass spectrometry (LC-MS) to the environmental analytical toolbox. Robust instruments typically using electrospray and atmospheric pressure chemical ionisation were well suited to the analysis of the more polar CECs, such as alternative antifouling biocides to TBT, pharmaceuticals, personal care products, veterinary medicines, illicit drugs and rodenticides. Robust analytical methodology is key to my research [2, 4, 18, 31, 34, 35, 42, 49, 66, 69, 72, 73, 86, 94, 102] as it allows the better understanding of how contaminants behave and interact with the environment. Development of robust, specific and sensitive methods for the analysis of alternative antifouling biocides [2, 4] allowed for the first time an evaluation of their life-cycle from release at the paint surface, and the factors that influence this [3], their occurrence in the environment [7, 8, 12, 29], fate and behaviour [12, 16] and subsequent effects [36, 41]. Assessment of the environmental risks based upon these data showed that both Irgarol 1051 and diuron were a threat to freshwater and marine algae. The significance of this research is that it subsequently led to restrictions being placed on the use of Irgarol 1051 and diuron in antifouling products in a number of European countries [58] and an awareness of the hazards associated with the deliberate release of biocidal products into the environment [86]. Observations of human pharmaceutical residues in the chromatograms of wastewater effluent samples being analysed by EDA and reports of their occurrence in German wastewaters motivated the development of LC- tandem MS methods for the quantification of pharmaceutical residues in waste- and surface waters [18]. Pharmaceuticals, we showed, occur in treated wastewater effluents and marine and freshwater recipients [24, 25, 30, 42, 43, 51, 66] and that, to no great surprise, the per capita pharmaceutical loads from hospitals were greater than the general population [43, 51]. Other highlights include understanding the processes that occur within sewer systems and what influences pharmaceutical occurrence in the final treated effluent [59, 60, 81, 85, 105], all of which allow for a better assessment of the overall risk posed to the environment. Even though several hundred papers have been published on pharmaceuticals in the environment since my early work, this has almost exclusively been focused on the parent pharmaceutical ingredient in aqueous matrices from developed counties. To remedy this shortfall more recent work has focused on quantifying the proportion of pharmaceutical metabolites released as compared to the parent [66], pharmaceutical occurrence in sludges and sediments [69], as well as evaluating occurrence in less studied water cycles [101].

The performance of public utilities in low-income countries with respect to service to all customers, and particularly lower-income urban consumers, is understood to be limited in many cases. The Government of Ghana chose to implement a private sector management contract in order to deliver significant change in service delivery and financial viability. The five year management contract with Aqua Vitens Rand Limited ran from 2006 to 2011 and was not renewed. This study investigates the public utility outcomes, both as a state owned corporation and a state owned limited liability Company, and compares those outcomes with the achievements of the private operator through a Management Contract. The latter two management models operated under the oversight of the newly formed economic regulator, the Public Utility Regulatory Commission in 1999 and any effect of that regulation is considered. The hypothesis of the study developed in 2008 was that “a management contract would not provide the necessary level of empowerment, incentives and commitment and access to resources for a private operator to adequately and efficiently perform even where there is an established economic regulator with a clear mandate”. The case study approach was employed for the study data was gathered on the operations, activities, regulation and management of the urban water utility through documentary review, key-informant interviews, household surveys, public hearing meetings and user observations. However, three major cities including Accra, Kumasi and Tamale were used for the household survey. These three cities were carefully picked out taking into account the political, economic, geographical, social and cultural significance that each of the them represents and commands in Ghana.

Les usines de traitement des eaux usées ne sont pas prévues pour traiter les polluants émergeants, substances organiques, tels des résidus de médicament, des produits phytosanitaires ou des hormones. Par conséquent, elles sont la source principale d’émission de micropolluants récalcitrants dans l’environnement. La Directive DCE 2000/60/CE demande un "bon statu chimique et biologique” de tous les plans d'eau d'ici 2015. L’objectif principal de cette thèse de doctorat a été d’adopter une méthode respectueuse de l’environnement pour traiter ces polluants. La méthode choisie est basée sur le processus d’oxydation avancée (POA). Elle se base sur la génération par voie solaire, et in situ, d’espèces radicalisées hautement réactives (HO● et/ou SO4-), en se focalisant sur la photocatalyse hétérogène et homogène. Les performances de l'POA ont été évaluées en comparant les taux de dégradation et/ou reminéralisassions des micropolluants. Ce critère a été complété par l'identification des sous-produits, de ses transformations associés et de mesures de toxicité. A cet effet, des tests standards d'écotoxicité ainsi que d'activité oestrogénique ont été réalisés, par la méthode toxicologique ISO ou par le test spécifique inhérent au contrôle de l’activité oestrogénique des eaux usées. Les technologies basées sur les processus d’oxydation avancée par voie solaire peuvent être des méthodes prometteuses de traitement des eaux usées. Toutes les molécules testées sont systématiquement dégradées, même celles présentes à de basses concentrations. La compatibilité environnementale a systématiquement été améliorée. L’irrigation des cultures en réutilisant des eaux usées devient possible. / Wastewater effluents are the major source of micropollutants in the environment. These recalcitrant compounds that can be escape from wastewater treatment plant (WWTP) are called emerging contaminants. It is necessary to improve the efficiency of wastewater treatment plants. In fact, Water Framework Directive required a “good chemical and biological status” of all water bodies until 2015. The major aim of the dissertation was to contribute to improve the evaluation of solar advanced oxidation processes, and more specifically heterogeneous and homogeneous photocatalysis, for removing emerging contaminants from wastewater effluents. In this objective, the efficiency of AOPS was not only evaluated with the degradation and/or mineralization rates of the micropollutants. This necessary criterion was completed with the identification of the by-products and the associated transformation pathways, but also with toxicity measurements. This last point was explored with standard ecotoxicity tests and also estrogenic activity that represent a specific test relevant to characterize an identified risk associated to the discharge of effluents into the environment.All the experimental results obtained during this dissertation tends to demonstrate that solar advanced oxidation processes has the potential to open new feasible remediation strategies for WWTPs effluent tertiary treatment before wastewater reuse in irrigation for instance. All the tested molecules have systematically been degraded, high number of micro-organic pollutants initially presented in a mixture were removed even at very low concentration, environmental compatibility is systematically improved.

This thesis describes both batch and continuous processes for water treatment by adsorption with electrochemical regeneration of the adsorbent using an airlift reactor. The process is based on the adsorption of dissolved organic pollutants onto a graphite intercalation compound (GIC) adsorbent and subsequent electrochemical regeneration of the adsorbent by anodic oxidation of the adsorbed pollutant. Batch experiments were carried out to determine the adsorption kinetics and equilibrium isotherm for a sample contaminant, the organic dye Acid Violet 17 on the GIC (Nyex®1000) adsorbent. The adsorption capacity was found to be around 1 ± 0.05 mg/g. The rate of adsorption appeared to follow pseudo-second order kinetics. The increase in the rate adsorption with temperature indicated an activation energy of around 4.2 KJ/mole, suggesting that the mechanism of adsorption was physisorption. It was demonstrated that the adsorbent could be regenerated by anodic oxidation of the adsorbed dye in a simple electrochemical cell. The GIC adsorbent recovered its initial adsorption capacity after 40 to 60 min of treatment at a current density of 10 mA/cm2, corresponding to a charge passed of 12 to 15 C/g of adsorbent. The charge passed is consistent with that expected for mineralisation of the dye suggesting that the dye was removed and destroyed with high charge efficiency. Experiments were carried out to investigate the characterisation and performance of the continuous process, where water is treated continuously in a fluidised adsorption zone and the adsorbent is circulated through a moving bed electrochemical regeneration cell. The adsorbent circulation rate, the residence time distribution (RTD) of the reactor, and water treatment performance by continuous adsorption and electrochemical regeneration were studied. The RTD behaviour could be approximated as a continuously stirred tank. It was found that greater than 90% removal at feed concentrations of up to 100 mg/L were achieved using a single pass through a large continuous treatment unit by adsorption and electrochemical regeneration with a flow rate of 0.25 L/min. In a smaller continuous treatment unit 98% removal at feed concentrations of up to 66 mg/L were achieved in a single pass with a flow rate of 0.24 L/min. Steady state and dynamic models have been developed for the continuous process performance, assuming full regeneration of the adsorbent in the moving bed electrochemical cell. Experimental data and modelled predictions (using parameters for the adsorbent circulation rate, adsorption kinetics and isotherm obtained experimentally) of the dye removal achieved were found to be in good agreement. A higher dye removal was found with a co-current PFR model, but a number of tank in series (n CSTRs) was found to give higher contaminant removal for the same total adsorption zone volume. It was also found that the predicted number of stages of batch adsorption / regeneration required to achieve 99.9% AV17 removal was halved when the adsorptive capacity of the adsorbent was doubled. Similarly the predicted number of continuous CSTR adsorption / electrochemical regeneration process units required in series to achieve 99% AV17 removal was reduced by more than two thirds when the adsorptive capacity of the adsorbent was doubled.

Management of water quality is generally based on physically-based equations or hypotheses describing the behaviour of water bodies. In recent years models built on the basis of the availability of larger amounts of collected data are gaining popularity. This modelling approach can be called data driven modelling. Observational data represent specific knowledge, whereas a hypothesis represents a generalization of this knowledge that implies and characterizes all such observational data. Traditionally deterministic numerical models have been used for predicting flow and water quality processes in inland and coastal basins. These models generally take a long time to run and cannot be used as on-line decision support tools, thereby enabling imminent threats to public health risk and flooding etc. to be predicted. In contrast, Data driven models are data intensive and there are some limitations in this approach. The extrapolation capability of data driven methods are a matter of conjecture. Furthermore, the extensive data required for building a data driven model can be time and resource consuming or for the case predicting the impact of a future development then the data is unlikely to exist. The main objective of the study was to develop an integrated approach for rapid prediction of bathing water quality in estuarine and coastal waters. Faecal Coliforms (FC) were used as a water quality indicator and two of the most popular data mining techniques, namely, Genetic Programming (GP) and Artificial Neural Networks (ANNs) were used to predict the FC levels in a pilot basin. In order to provide enough data for training and testing the neural networks, a calibrated hydrodynamic and water quality model was used to generate input data for the neural networks. A novel non-linear data analysis technique, called the Gamma Test, was used to determine the data noise level and the number of data points required for developing smooth neural network models. Details are given of the data driven models, numerical models and the Gamma Test. Details are also given of a series experiments being undertaken to test data driven model performance for a different number of input parameters and time lags. The response time of the receiving water quality to the input boundary conditions obtained from the hydrodynamic model has been shown to be a useful knowledge for developing accurate and efficient neural networks. It is known that a natural phenomenon like bacterial decay is affected by a whole host of parameters which can not be captured accurately using solely the deterministic models. Therefore, the data-driven approach has been investigated using field survey data collected in Cardiff Bay to investigate the relationship between bacterial decay and other parameters. Both of the GP and ANN models gave similar, if not better, predictions of the field data in comparison with the deterministic model, with the added benefit of almost instant prediction of the bacterial levels for this recreational water body. The models have also been investigated using idealised and controlled laboratory data for the velocity distributions along compound channel reaches with idealised rods have located on the floodplain to replicate large vegetation (such as mangrove trees).