The complexity of cementitious matrices and their application in the immobilisation of radioactive waste has led to detailed examination of their ability to condition permeating water to high pH by both experimental and thermodynamic studies. This thesis considers the stability and solubility of pure hydrate phases: Ca(OH)₂; CaO-SiO₂-H₂O gel, Ca:Si = 0.85, 1.1, 1.4, 1.8; 3CaO.Al₂O₃.6H_zO; 3CaO.Al₂O₃.CaSO₄.12H₂O and 3CaO.Al₂O₃.3CaSO₄.32H₂O, and the phase formation and stability within CaO-SiO₂-CaCO₃-H₂O and CaO-Al₂O₃-SiO₂-H₂O compositions aged in saline solutions, up to 1.5M NaCl and 0.05M MgSo₄, at 25°, 55° and 85°C. The two main high pH conditioning phases of cementitious systems are Ca(OH)₂ and C-S-H gel. Sodium chloride enhances the solubility of Ca(OH)₂ and causes a slight reduction in the Ca:Si ratio of C-S-H gels by the progressive leaching of calcium. Silicate polymerisation within C-S-H phases is inhibited by sodium chloride though it is uncertain how this alters the crystallisation kinetics. The pH buffering capacity is maintained when aged in sodium chloride concentrations 0.5, 1.0 and 1.5M at 25°, 55° and 85°C. The stability of calcium sulfoaluminate aged in sodium chloride is greater than of 3CaO.Al₂O₃.6H₂O, which is unstable with respect to 3CaO.Al₂O₃.CaCl₂.10H₂O in NaCl < 0.5M. These phases undergo a progressive phase change to the 3CaO.Al₂O₃.0.5CaSO₄.0.5CaCl₂.10-12H₂O and 3CaO.Al₂O₃.CaCl₂.10H₂O at increasing aqueous Cl:SO₄ ratios. The formation of a limited solid solution region within 3CaO.Al₂O₃.xCaSO₄.l-xCaCl₂.yH₂O: 0.00 ≤ SO₄:Cl ≤ 0.06, was characterised. In magnesium sulfate, 5 - 50m.mol/l, calcium within hydrate phases is progressively replaced by magnesium with formation of Mg(OH)₂, MgO-SiO₂-H₂O gel, 4MgO.Al₂O₃.xH₂O and gypsum. The pH conditioned by the resultant solid assembly decreases to less than that desirable for containment of radioactive waste, to < 9. Consideration of the phase formation and persistence within the CaO-SiO₂-CaCO₃-H₂O and CaO-Al₂O₃-SiO₂-H₂O systems was examined in solutions containing both sodium chloride and magnesium sulfate. The chemical interactions observed were dominated by the replacement of calcium by magnesium within the solid phases with the formation and persistence of mixtures of Mg(OH)₂, MgO-SiO₂-H₂O gel and gypsum. At low Mg:Ca-CO₃ ratios the persistent stability of gehlenite hydrate at 25°C was observed in appropriate samples. The chemistry of the aqueous phase is dependent on the Mg:Ca-CaCO₃ ratio as well as the Ca:Si ratio. At high Mg:Ca-CaCO₃ ratios the high pH conditioning properties are destroyed and buffering occurs at a value below pH 9.

This study aims to determine the factors that affect the implementation of marine pollution policy, especially with regard to regulation of the hazardous substances which contaminate the marine environment- The purpose is to identify weaknesses in the current regulatory regime and to propose improvements. The study also aims to develop a new strategic framework for the implementation of the recent international policy commitments, which call for the complete cessation of discharges of hazardous substances into the marine environment by the year 2020. Furthermore, the study seeks to provide evidence to support or challenge current theories relating to regulation and policy implementation. Examination was made of the attitudes of environmental managers from the UK chemical industry and inspectors from the environmental agencies towards the regulatory system. These are the key personnel who operate at the regulatory interface where the policy outcome is determined. The methodology combined both qualitative and quantitative techniques. Structured interviews helped define the issues for subsequent investigation using a questionnaire survey which was sent to over 700 key personnel. Focus groups were then used to explain the survey findings and develop solutions to key regulatory problems. Statistical analysis of the survey response data revealed similarities and significant differences between the views of industry and the regulator on the effectiveness of the current Integrated Pollution Control regime. The strength of the system was perceived as its practical and pragmatic approach, coupled with a convenient and familiar bureaucracy. The weaknesses identified related to the derivation and enforcement of standards. The Environmental Quality Standards system, which underpins the regime, was acknowledged to be flawed by both operators and regulators who agreed it should be improved by the expansion in the number of priority listed chemicals, the introduction of sediment Environmental Quality Standards and Direct Toxicity Assessment of effluents. Focus groups supported the expansion of the system, but recognised that it would create a regime that was both complex and impractical. The findings were used to construct a revised model of the existing regime. Multivariate analysis of the industry response data identified 3 cluster types and significant differences were revealed between their knowledge of policy developments, their implications and the need for changes to the current system of hazardous chemical control. Operators and regulators acknowledged the existence of the mutual interdependency which has created and maintained a tight policy network (community) at the regulatory interface. Further evidence to support the existence of this community and of regulatory capture, was provided by the study data. Focus group discussions also identified the requirement for a more fundamental reappraisal of the regulatory system in order to deliver the OSPAR strategy. A new regulatory model, which incorporates process and product substitution, is proposed as a strategic framework to ensure that future policy commitments are implemented. This approach may lead to the opening up of the current tight policy network with resultant benefits for policy implementation and reduced regulatory capture. The new model could be applied by other countries within the OSPAR region and in other regions of the world, in order to improve environmental protection.

No description available.

The use of active carbon (AC) as a potential adsorbent for the removal of uranium from aqueous solution has been investigated. Two principal areas have been studied i.e. uranium adsorption from near-neutral and dilute acidic solutions and uranium adsorption from concentrated acid solutions. The aqueous solution matrix used was nitric acid. In the former case commercial (as-received) and oxidized active carbons were investigated. It was noticed that oxidation of as-received ACs with nitric acid solution significantly improves the adsorption capacity of uranium from both near-neutral and dilute acidic solutions. Oxidized ACs were particularly effective in dilute acidic solution , whilst as-received ACs have shown little uranium sorption. Batch equilibrium isotherms were constructed to compare the adsorption capacities of as-received and oxidized ACs. The batch kinetics of uranium adsorption was studied and a column experiment was performed.

Inorganic colloids are considered as potential transporters of toxic metals in the geosphere. If inorganic colloids are stable and able to adsorb toxic metals they may enhance their apparent solubility. If these colloids are mobile in the aquatic environment they may also enhance the transport of toxic metals. It is therefore of considerable interest to determine the characteristics of inorganic colloids in relation to toxic metal transport.

No description available.

No description available.

The performance of a growing sulphate reducing bacteria consortium for Sr2+, Co2+ and Cs+ removal from solution in a batch sulphidogenic bioreactor was investigated. Metal removal by the growing bacterial consortium, and microbial culture growth and metabolic activities (biological sulphate removal) were continuously monitored in the bioreactors over the duration of the treatment period. On the other hand, diversity changes within the bacterial consortium before and after bioreactor operation (28 days) were performed using the partial 16S rRNA fingerprinting method. In the original bacterial consortium, Enterococcus and Staphylococcus sp. were the dominant bacterial species. However, the presence of Sr2+, Co2+ and Cs+ in the growth media, resulted in the emergence of new bacterial species belonging to the Citrobacter, Paenibacillus, and Enterococcus and Stenotrophomonas genera, respectively. The Citrobacter and Paenibacillus sp. demonstrated high tolerance towards the presence of the divalent cations, Sr2+ and Co2+, respectively, while the Enterococcus and Stenotrophomonas sp., demonstrated Cs+ high tolerance. The bacterial growth and sulphate removal rate were significantly decreased at initial metal ion concentrations ≥100 mg/L. The toxicity and inhibitory effects of the metals on the present SRB consortium was observed in the order Sr>Co>Cs. The metal uptake capacity (qτ) of the bacterial consortium decreased with increasing initial metal concentration, and complete Sr2+, Co2+ and Cs+ removal was observed at initial metal concentrations ≤75 mg/L. Overall, the present SRB consortium demonstrated a superior Sr2+ removal capacity (qmax= 405 mg/g), and the least for Cs2+, where qmax = 192 mg/g. The present SRB culture exhibited a superior Sr+ and Cs+ binding capacity, compared to other studies in literature. Results from Sr2+, Co2+ and Cs+ biosorption kinetics indicate that initial concentration and solution pH played a vital role in determining the rate of metal removal kinetics. The experimental data was successfully analysed by the pseudo-second-order rate model, demonstrating that chemisorption is the main rate limiting step for the removal of Sr2+, Co2+ and Cs+ from solution. In this study, the adsorption behaviour of protons and of Sr2+, Co2+ and Cs+ onto the bacterial consortium cell surfaces was evaluated under anaerobic conditions as a function of pH (4-10), ionic strength (0.01, 0.05, 0.1M) and temperature (25, 50 and 75°C). Acid-base titrations of the bacterial suspension indicated that the titration data could be adequately described by a four site non-electrostatic model, with pKa values of 4.41, 6.69, 8.10 and 10. The Sr2+, Co2+ and Cs+ adsorption data could be fitted with a two site non-electrostatic model, involving the type 1 and 2 sites (carboxylic and phosphoryl sites). Increasing the ionic strength had a negative effect on the adsorption of metal ions from solution. There was no observed temperature dependence on the adsorption of Co2+ and Cs+ from solution. In summary, results obtained in this study have shown that the processes involved in microbial Sr2+, Co2+ and Cs+ removal from contaminated sources is a direct function of the microbial characteristics and efficiency, mass transfer and surface complexation effects under varying environmental conditions. One important goal to be achieved in future studies will be the determination of the intrinsic stability constants and the structure of the formed metal complexes species. These constants can be used directly in risk assessment programs. / Thesis (PhD(Eng))--University of Pretoria, 2011. / Chemical Engineering / unrestricted

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The nuclear industry faces important technical challenges for HLW storage and designing new nuclear fuels. Such materials have to perform under severe conditions and accommodate defects safely. Few materials are suitable for those purposes but certain types of ceramics are promising candidates; among them oxide compounds such as pyrochlores and zirconolites. The aim of this PhD project was to synthesise novel actinide oxide particles, in which two different approaches were taken: controlled hydrolysis and solid state chemistry. Some minerals were naturally doped with actinides and rare earth elements and inspired synthetic formulations of new targeted waste forms for High Level Waste (HLW) instead of other disposal routes. The choice of synthetic pyrochlore and zirconolites as actinide hosts was inspired by the existence of naturally occurring actinide rich minerals. Substitutions within the cubic Y2Ti2O7 were investigated via the respective Y2Ti2-2xFexNbxO7 and Y2-xCexTixFexO7 solid solutions.Controlled hydrolysis was based on previous work with Lewis acidic transition metal cations. It was shown that it was possible to control the hydrolysis products in the presence of chelating organic ligands by carefully controlling the experimental conditions of the system. The same principles should apply to the chemistry of the actinide ions as they too are Lewis acidic. Such chemistry has implications for understanding the behaviour of actinides in nuclear processes within aqueous and organic systems. This project was a collaboration between Sheffield University (Immobilisation Science Laboratory, ISL) and The University of Manchester (Centre for Radiochemistry Research, CRR) through the DIAMOND (Decommissioning Immobilisation and Management of Nuclear waste for Disposal) University research consortium.