The gas chromatograms of crude oil hydrocarbons reveal both resolved and unresolved components. The unresolved feature is commonly referred to as the unresolved complex mixture (UCM). UCMs are thought to result from the co-elution of complex mixtures of hydrocarbons with similar chemical properties and become more obvious as resolved components are removed by processes such as weathering and refining. Consequently UCMs are a prominent feature in oil-polluted sediments, biodegraded crudes and refineiT products. The characterisation of both aliphatic and aromatic unresolved complex mixtures (UCMs) of hydrocarbons, as well as their possible effects on the environment, is described. An aliphatic hydrocarbon UCM isolated from the base oil of Silkolene 150 lubricating oil was characterised by a combination of micro vacuum-distillation and oxidative degradation. Vacuum-distillation produced six distillate cuts and a residue which were all highly unresolved by GC (ca. 951/6). The average molecular weight of each cut was determined by probe CIMS (310 - 440 Daltons), and varied by -20 Daltons. Cr03 oxidation of each fraction yielded similar distributions of n-monocarboxylic acids, ketones and lactones as well as C02 (ca. 6%). The resolved products of oxidation suggest that the aliphatic UCM is a rather homogeneous mixture of highly branched alkanes. However a significant amount of the products remain unresolved (UCMox.; ca. 70-95%). A retro -structural analysis approach, using an aromatic UCM oxidant (Ru04), combined with a mass balance approach, was used to characterise aromatic UCMs. Following reproducibility studies and the analysis of authentic aromatic compounds, the method was applied to the characterisation of unresolved aromatic refinery oil fractions and a suite of aromatic UCM distillate fractions. Selected refinery oils were separated into mono-, di-, tri- and tetraaromatics by BPLC and shown to be mainly unresolved by GC (ca. 80%). Ru04 oxidation of these fractions yielded DCM soluble products (24 - 74%), water soluble products (0 - 10%) and C02 (12 -78%). The principal resolved products in each oxidation were monocarboxylic acids and dicarboxylic acids which were used to reconstruct precursor compounds. Vacuum-distillation of Tia Juana Pesado crude (Venezuela) gave six cuts and a residue which were analysed by GC, 1H NMP, UV and probe CIMS to obtain molecular weight (171 - 301 Daltons) and broad structural information whilst Ru04 oxidation was used to obtain molecular information via the retro -structural analysis approach. This showed that the aromatic UCM was in fact highly aliphatic and contained alkyl and cycloalkyl tetralins. A significant advancement in the quantitative characterisation of UCMOx. and subsequently the characterisation of aromatic UCMs was made. Ion cyclotron resonance spectrometry (ICR) was used to characterise the Ru04 oxidation products of selected refinery fractions. Analysis of the oxidation products of a monoaromatic refinery fraction indicated the presence of monocarboxylic acids (Cl - C21; 58%) and alicyclic carboxylic acids (C7 - C19; 16%), a hydrogenated monoaromatic sample contained monocarboxylic acids (Cl - C20; 30%), dicarboxylic acids (C2 - C11,7%) and alicyclic carboxylic acids (C7 - C18; 11%) , whilst a diaromatic fraction contained monocarboxylic acids (C10 - C19; 7%), alkyl phthalic acids (C8 - C17', 17%) and cycloalkyl phthalic acids (C11 - C15; 3%). Retro -structural analysis suggests that the nonhydrotreated monoaromatic UCM is mainly comprised of alicyclic and alkyl substituted benzenes, the monoaromatic UCM isolated from the hydrotreated oil of alky'l and cycloalkyl substituted tetralins and the diaromatic fraction of alkyl and cycloalkyl naphthalenes. This was supported by, FIMS analysis of the fractions prior to oxidation. As an investigation of the environmental toxicity of UCMs, the effect of a saturated aliphatic UCM, and its chemical oxidation products, on the feeding rate of mussels (Mytilus edulis), was investigated. The UCM had little effect, whilst oxidation resulted in an increase in toxicity. The non-toxic nature of the hydrocarbons was attributed to their low aqueous solubility, whilst oxidation resulted in the formation of products NNith a greater solubility, which were sufficiently hydrophobic to be narcotic toxicants. Parts of this work have been published [Thomas et al., (1993) Organic Geochemistry, Falch Hurtigtrykk, Non%-ay(A bstract), 717-719; Thomas et al., (1995) [Vater Research. 29,371-382]. iv

The feasibility of improving water quality by food web manipulation in an urban eutrophic tropical reservoir, Lago Paranoa (Brasilia, Brazil) was investigated. The potential of promising biomanipulation strategies was experimentally tested in limnocorrals: reduction of internal nutrient loading by controlling tilapia overpopulation, and suppression of nuisance cyanobacteria by stocking non reproducing filter-feeding silver carp. A four-month test in two large littoral isolated areas of the reservoir (1,000 m2 each) stocked with high vs. low tilapia biomass revealed that fish over-population promoted blooms of Microcystis and decreased water clarity by supplying phytoplankton with additional nutrients (mainly phosphorus, "P"). Since reduction of tilapia biomass from 150 to 40 g/m3 resulted in significant water quality improvements, the release of commercial fisheries using cast-nets was recommended. Field experiments III floating net-cages (10 m3) were conducted to evaluate silver carp adaptation to Lago Paranoa and to determine fish growth rates when maintained feeding exclusively on the abundant plankton in the reservoir. High growth rates (up to 6 g/day) and survivorship (> 90%) of young-of-the-year (72 g), juveniles (300 g) and adult silver carp (1100 g) during both dry and rainy season were observed. Efficient ingestion of nuisance algae was evidenced by the dominant presence of Microcystis aeruginosa and Botryococcus braunii colonies in the fore-intestine of experimental fishes. Results indicate the great potential for silver carp cage culture as a low-cost and environmentally beneficial economic activity. Following indications from literature and previous studies in Lago Paranoa, the optimum range of silver carp biomass which maximize phytoplankton control was determined in ten large replicated limnocorrals (50 m3 ). Although a significant decrease in Microcystis abundance was achieved by stocking silver carp at all biomass levels, net-phytoplankton biomass was only significantly suppressed at moderate fish stocking densities of 40 and 60 g/m3 . Two additional limnocorral experiments during dry and rainy seasons were performed to test the effectiveness of both biomanipulation strategies when adopted separately or simultaneously. Water quality improvements through control of tilapia abundance (from 100 to 40 g/m3) and stocking with silver carp (at moderate stocking rates of 40-50 g/m3) induced significant decreases in total phosphorus (21- 31 %), cyanobacteria density (40-44%) and phytoplankton biomass (22-38%). As those strategies were found to act independently, the combination of both enhanced water quality benefits by reducing total phosphorus by 38%, cyanobacteria density by 75% and phytoplankton biomass by 60%. To predict the internal P-loading reduction that could be achieved by implementing both biomanipulation strategies on a whole-reservoir scale, P excretion rates were quantified in indoor tanks for 16 and 40 g tilapia (0.527-1.576 ug SRP/g ww/h) and silver carp (0.391-0.737 ug SRP/g ww/h). It was estimated that the tilapia contribution to internal P-Ioading (5.4 mg TP/m2/day for 1,300 kg/ha) is equivalent to external P input to the Bananal Branch (6.0 mg TP/m2/day). A 60% reduction in tilapia biomass plus stocking of silver carp at densities of up to 60 g/m3 after three years would not change internal P-Ioading (5.6 mg TP/m2/day) but would (1) reduce by 60% the input of "new" phosphorus to the water column from tilapia bottom feeding, and (2) increase grazing on phytoplankton following silver carp introduction.

The limited underground water resources and the dramatic increase of fresh water consumption in Qatar forced the government to seek alternative ways to compensate for the lack of fresh water resources. Unfortunately, most of the currently available alternatives are costly in terms of excessive fuel consumption; also they require large capital investment and high maintenance cost. Such plants currently produce over 98% of the total fresh water in Qatar. This ratio may increase to 100% in the next few years. The main aim of this work is to investigate the most viable water desalination processes, which can produce sufficient, and a continuous supply of fresh water with low operation and construction costs. Climatic conditions and solar radiation in Qatar have been studied and analysed to determine the performance of any potential solar system applicable to this country. A technical and economical investigation into the current and common desalination methods with particular emphasis on the three main desalination systems including multistage flash, multiple effect distillation and reverse osmosis were conducted and included. A comprehensive literature survey on various water desalination methods was undertaken. The current experimental program was confined mainly to one novel type of tilted tray solar still system, namely pyramid tilted tray solar still, which was developed to increase productivity by increasing the receiving surface area of the still (the absorber) in order to collect the optimum amount of solar radiation. Two types of cover have also been selected and tested in this work, namely pyramid and dome shapes. These tilted tray solar stills were designed and constructed on a small scale and have been tested under controlled laboratory conditions at the University of Hertfordshire. Various parameters, which are likely to effect the still performance have been investigated. These include water flow rate, spacing between cover and tray surface, glass thickness, insulation layer, and inlet water temperature. Finally, a comparison of the stills performance characteristics of the two shapes has been carried out. The laboratory experimental results of hourly production revealed that pyramid type solar still yield higher distilled water output results than the dome type. However, the use of the pyramid shape with tilted tray solar can lead to further increase in the still productivity by optimising the orientation and surface area of the still absorber. The field experimental results of pyramid solar still, which were conducted under local climate conditions of Qatar, indicated clearly that solar desalination can be a suitable economical option, particularly for remote areas, where the fresh water demand is low and water transport is expensive. Moreover, a theoretical model was employed to predict the effects on solar still performance under three various parameters under typical climatic conditions of Qatar; These include the thermal insulation layer, the water depth and wind speed. Due to the economical reasons the dual-purpose multistage flash process will remain for the foreseeable future the preferred process, when fresh water and electricity demands are growing concurrently and rapidly.

For sustainable water management, here is a necessity to consider alternatives, in addition to conventional systems. The aim of this research is to develop and demonstrate a sustainables, from and greywater reclamation system for WC flushing and it was started in 1994. In the UK there are no water quality standards for WC flushing water use. There were no design guidelines for greywater water reclamation and no published study on the supply-dernandb alance, in detail, for water recycling in institutions such as universities. The research has shown the feasibility of planned direct grey and storm water reclamation and recycling system to manage growing water and wastewater problems. This thesis is based on the information gathered from 4 universities, 3 hotels and 3 recreational centres, and experiences gained at Loughborough University during the development and demonstration of the full scale "in-house grey and roof water" reclamation and recycling systems. The water use, greywater quality and roof water characteristics were studied in detail and this information was used for the development of the reclamation and recycling system. The studies showed that the water usage at the university halls were not similar to usage in households. Unlike large water supply schemes, small in-house systems generate a large peak factor for water use. To avoid deficit, in addition to personal washing waters, a top-up of laundry wastewater or roof water, and a well-designed balancing tank is necessary. The demonstration study shows that there was no standby mains' water used, which means that the water reclaimed was sufficient for reuse. The quality characterisation study shows that the greywater and first flush storm water roof runoff were polluted. The characteristics of combined grey and roof water are suitable for biological treatment. Based on the infomation, a lab-scale unit was developed; the reactor characteristics and performance such as head losses and removal efficiency were monitored; and the unit was refined. Two novel multi-barrier reclamation systems were developed to achieve sufficient quantity and near potable quality of water with minimum maintenance and cost. During 1997 the grey and roof water recycling system with laboratory tested physical and biological reclamation processes without the use of coagulants and disinfection were installed. The performance of the treatment system was closely monitored until 1998. This provided benefits in near potable quality of reclaimed water, low head loss, reliability, failure free operation and simple maintenance. The reclaimed effluent from Project I and 2 met the UK/EU bathing water standards and was also able to meet the US EPA standards for WC flushing. The microbial (using coliform as an indicators) quality of reclaimed water without disinfection is acceptable for controlled recycling systems (carefully monitored and fully informed). There were no odour problems in the treated water or sludge blockages. Comparatively, Project I was more efficient at removing coliform, turbidity, solids (suspended, dissolved, volatile), and Project 2 better at removing carbon (organic and inorganic). A simple cost benefit analysis done for the recycling system at Royce Hall of Residence showed 10 years pay back. More detailed cost-benefit analysis including comparisons of new built and retrofit recycling system and fife cycle analysis are recommended. This study shows that most of the people questioned were accepted and were willing to consider using the recycling system for toilet flushing, if the water was clear, colourless, odour free, carried no risk and gave cost-benefits. During the demonstration stage the users willingly accepted non-potable grey water reuse.

No description available.

This research focuses on the development, evaluation, and application of a mercury (Hg) mass balance model for predicting the accumulation of Hg in fish. This model requires accurate estimates of Hg elimination rate by fish and feeding rates to adequately predict Hg concentration in fish. An empirical model was developed to estimate Hg elimination by fish using data obtained from published experiments. This analysis showed that Hg elimination rate was overestimated in short-term experiments, positively correlated to water temperature, negatively correlated to body size, and that the elimination rate of inorganic Hg was faster than that of methylmercury. This empirical model was then incorporated in a Hg mass balance model to predict the concentration of Hg in fish. The Hg mass balance model accurately predicted Hg concentration in fish when it was combined with food consumption rates that were determined using a radioisotopic method. This analysis suggested that the parameters of the Hg mass balance model were adequate for predicting Hg concentration in fish. I also showed that Hg concentration tended to be underestimated by the Hg mass balance model when it was combined with feeding rates determined with a laboratory-derived bioenergetic model, probably because activity costs derived in the laboratory do not reflect activity costs of fish in the field. Beside predicting Hg concentration in fish, I showed that this mass balance model could also be used to estimate feeding rates of fish in the field by measuring the concentration of Hg in fish. This approach was validated using data obtained from a published experiment. It was also successfully tested using independent estimates of feeding rates obtained with a radioisotopic method. I applied this Hg mass balance model to compare the energy budget of sympatric populations of dwarf and normal whitefish (Coregonus clupeaformis). This analysis showed that dwarf whitefish consumed 40--50% more food than normal whitefi

The research presented in the thesis develops an approach for the estimation and mapping of pollutant spreading in catchments and the associated uncertainty and risk of pollution. The first step in the approach is the quantification and mapping of statistical and geographical distributions of advective solute travel times from pollutant input locations to downstream recipients. In the second step the travel time distributions are used to quantify and map the spreading of specific pollutants and the related risk of water pollution. In both steps, random variability of transport properties and processes is accounted for within a probabilistic framework, while different scenarios are used to account for statistically unquantifiable uncertainty about system characteristics, processes and future developments. This scenario approach enables a transparent analysis of uncertainty effects that is relatively easy to interpret. It also helps identify conservative assumptions and pollutant situations for which further investigations are most needed in order to reduce the uncertainty. The results for different investigated scenarios can further be used to assess the total risk to exceed given water quality standards downstream of pollutant sources. Specific thesis results show that underestimation of pollutant transport variability, and in particular of those transport pathways with much shorter than average travel times, may lead to substantial underestimation of pollutant spreading in catchment areas. By contrast, variations in pollutant attenuation rate generally lead to lower estimated spreading than do constant attenuation conditions. A scenario of constant attenuation rate and high travel time variability, with a large fraction of relatively short travel times, therefore appears to be a reasonable conservative scenario to use when information is lacking for more precise determination of actual transport and attenuation conditions.

The development of Environmentally Adapted Lubricants (EALs) and their use has been gaining momentum over the last decade. It has been shown that raw EALs degrade in the environment in about one tenth the time of an equivalent mineral based lubricant. Estimates and findings such as these serve to highlight the potential benefits of the EAL products, it is also important however to investigate the by-products of their use to ensure that the benefits are not cancelled by an increase of, for instance, combustion by-products. This thesis compares the emissions from a two-stroke outboard engine when using an EAL and an equivalent mineral lubricant, where the primary objective of the study is to characterise and quantify the pollutants that remain within the water column after combustion. To accomplish this, tests were conducted both in the laboratory (freshwater) and in the field (seawater) for a range of throttle settings. A 1.9kW two-stroke outboard engine was set-up in a test tank and water samples were taken from the tank after the engine had been run for a period at each of the throttle settings. The tests were repeated for a 5.9kW four-stroke engine, however, the experiments were only conducted in the laboratory (freshwater) and using only a standard mineral lubricant. Statistical analyses of the results were conducted using a Principal Components Analysis (PCA). A simple dilution model was used to estimate the initial outboard engine emission concentrations, which was extended to determine the concentrations at distances of 1, 10 and 100 metres from the source. An investigation of the Total Toxicity Equivalence of the PAH pollutant concentrations (TEQPAH) was conducted using Toxicity Equivalent Factors (TEFs). Results for both types of engine and in both fresh and seawater showed that even the initial concentrations at the source, in almost all instances, were well below the ANZECC water quality guidelines trigger levels. At a distance of 1 metre from the source all concentrations were well below, and therefore, the Total Toxicity Equivalents of the PAHs were found to be even lower. It is concluded that the emissions from a single outboard engine when using either an EAL or a mineral based lubricant are similar. However, the use of EALs has further reaching advantages in that spilt raw lubricants will degrade in the environment up to 10 times faster than a mineral lubricant. Also EALs are less toxic to aquatic and marine organisms and therefore the benefits of using them has to be viewed from a wider perspective. The results in this thesis for a single outboard engine now form the basis for a more detailed environmental assessment of their impacts.

Research Doctorate - Doctor of Philosophy (PhD) / Shrimp farming and capture fishery are two of the major industries of Can Gio district, Ho Chi Minh City, southern Vietnam. These industries have recently developed and contributed to the improvement of local economy. However, they have also raised environmental concerns regarding water pollution and fish stock depletion. The negative impacts of shrimp farm effluents on the water quality of mainstream rivers and fish communities have not been studied in Can Gio. Additionally, there is a lack of research on the influence of the current fisheries management on environmental protection and fish conservation in this district. The goal of this study was to address key issues in fisheries management in Can Gio in regard to the impacts of wastewater from shrimp farming on the water quality of mainstream rivers that affect the local fish communities, and the influence of improper fishing practices that lead to the depletion of local fish stocks. This study also aimed to propose strategies to improve the local fisheries management for more environmentally responsible productions. Two mainstream surveys were developed to obtain data, i.e. environmental surveys for the assessment of water quality and pollution impacts on fish communities; and people interviews for the examination of fisheries management related to shrimp farming and fishing practices. The findings were used as a baseline to develop appropriate strategies for improving the management in terms of promoting sustainable productions both in shrimp farming and capture fishery industries and protecting the environment. This study found that shrimp farming, especially intensive farms have contributed to water pollution in mainstream rivers in Can Gio, and in turn the water pollution has adversely affected the local fish communities. The waters adjacent to the intensive farms were contaminated with high concentrations of organic matter. The number of fish species reduced and tolerant species appeared at higher proportions in these areas. Many improper practices in shrimp farming and fishing as well as weaknesses in government management were addressed to be the key issues leading to environmental pollution and fish depletion. The proposed strategies focused on improving the management at both government and community levels. Promoting community-based management was suggested as a key to the success in fisheries management in Can Gio.

Research Doctorate - Doctor of Philosophy (PhD) / Shrimp farming and capture fishery are two of the major industries of Can Gio district, Ho Chi Minh City, southern Vietnam. These industries have recently developed and contributed to the improvement of local economy. However, they have also raised environmental concerns regarding water pollution and fish stock depletion. The negative impacts of shrimp farm effluents on the water quality of mainstream rivers and fish communities have not been studied in Can Gio. Additionally, there is a lack of research on the influence of the current fisheries management on environmental protection and fish conservation in this district. The goal of this study was to address key issues in fisheries management in Can Gio in regard to the impacts of wastewater from shrimp farming on the water quality of mainstream rivers that affect the local fish communities, and the influence of improper fishing practices that lead to the depletion of local fish stocks. This study also aimed to propose strategies to improve the local fisheries management for more environmentally responsible productions. Two mainstream surveys were developed to obtain data, i.e. environmental surveys for the assessment of water quality and pollution impacts on fish communities; and people interviews for the examination of fisheries management related to shrimp farming and fishing practices. The findings were used as a baseline to develop appropriate strategies for improving the management in terms of promoting sustainable productions both in shrimp farming and capture fishery industries and protecting the environment. This study found that shrimp farming, especially intensive farms have contributed to water pollution in mainstream rivers in Can Gio, and in turn the water pollution has adversely affected the local fish communities. The waters adjacent to the intensive farms were contaminated with high concentrations of organic matter. The number of fish species reduced and tolerant species appeared at higher proportions in these areas. Many improper practices in shrimp farming and fishing as well as weaknesses in government management were addressed to be the key issues leading to environmental pollution and fish depletion. The proposed strategies focused on improving the management at both government and community levels. Promoting community-based management was suggested as a key to the success in fisheries management in Can Gio.