This work focuses on diffusion and advection through cementitious media, the work arises from two research contracts undertaken at Loughborough University: Experiments to Demonstrate Chemical Containment funded by UK NDA and the SKIN project, funded by the European Atomic Energy Community's Seventh Framework Programme. Diffusion will be one of the most significant mechanisms controlling any radionuclide migration from a nuclear waste, deep geological disposal facility. Advection may also occur, particularly as the immediate post closure groundwater rebound and equilibration proceeds but is expected to be limited by effective siting and management during the operational phase of the facility. In this work advection is investigated at laboratory scale as a possible shorter timescale technique for providing insight into the much slower process of diffusion. Radial techniques for diffusion and advection have been developed and the developmental process is presented in some detail. Both techniques use a cylindrical sample geometry that allows the radionuclide of interest to be introduced into a core drilled through the centre of the test material. For diffusion the core is sealed and submerged in a container of receiving solution which is sampled and analysed as the radionuclide diffuses into it. For advection, a cell has been designed that allows inflow via the central core to pass through the sample in a radial manner and be collected as it exits from the outer surface. The radionuclide of interest can be injected directly into the central core without significant disturbance to the advective flow. Minor improvements continue to be made but both techniques have provided good quality, reproducible results. The majority of the work is concentrated on a potential cemetitious backfill known as NRVB (Nirex Reference Vault Backfill) this is a high porosity, high calcium carbonate content cementitious material. The radioisotopes used in this work are 3H (in tritiated water), 137Cs, 125I, 90Sr, 45Ca, 63Ni, 152Eu, 241Am along with U and Th salts. In addition the effect of cellulose degradation products (CDP) on radioisotope mobility was investigated by manufacturing solutions where paper tissues were degraded in water, at 80°C, in the absence of air and at high pH due to the presence of the components of NRVB. All diffusion experiments were carried out under a nitrogen atmosphere. All advection experiments were undertaken using an eluent reservoir pressurised with nitrogen where the system remained closed up to the point of final sample collection. Results for tritiated water and the monovalent ions of Cs and I were produced on a timescale of weeks to months for both diffusion and advection. The divalent ions of Sr, Ca and Ni produced results on a timescale of months to years. Variations of the experiments were undertaken using the CDP solutions. The effects of CDP were much more apparent at radiotracer concentration than the much higher radiotracer with non-active carrier, concentration. In the presence of CDP Cs, I and Ni were found to migrate more quickly; Sr and Ca were found to migrate more slowly. Additional Sr experiments were undertaken at elevated ionic strength to evaluate the effect of the higher dissolved solids content of the CDP solutions. Some of the results for HTO, Cs, I and Sr have been modelled using a simple numerical representation of the system in GoldSim to estimate effective diffusivity and partition coefficient. The diffusion model successfully produced outputs that were comparable to literature values. The advection model is not yet producing good matches with the observed data but it continues to be developed and more processes will be added as new results become available. Autoradiography has been used to visualise the radionuclide migration and several images are reproduced that show the fate of the radiotracers retained on the NRVB at the end of the experiments. As the experimental programme progressed it was clear that results could not be produced in a suitable timescale for Eu, Am U and Th. These experiments have been retained and will be monitored every six months until either diffusion is detected or the volume of receiving liquid is inadequate to ensure the NRVB is saturated.

An extensive series of experimental tests were carried out at the Sheffield municipal solid waste incinerator plant (30 MW) from September 1988 to July 1989 to investigate the influence of the design and operating parameters on the performance of the incinerator which burns domestic and commercial wastes (500 ton/day). The following measurements were made around the plant: temperature measurements, pressure measurements, flue gas composition analysis and determination of physical and chemical properties of Sheffield refuse. Several other miscellaneous measurements were also made to monitor the effect of variation of operating parameters on the performance characteristics of the incinerator. A combustion model of Essenhigh type was then employed to model the combustion processes inside the solid refuse bed on top of the travelling grate. In addition a mathematical model of the finite difference type (FLUENT) was used to predict the three dimensional reacting flows (gaseous phase) within the incinerator geometry. Experimental measurements of gas composition, temperature and exit velocity were compared with model predictions. Modelling results were generally in good agreement with measurements. As a result of the test data and the mathematical modelling of the whole process, suggestions for design improvements for the Sheffield municipal solid waste incinerator were made which will substantially increase the efficiency, reduce emissions of pollutants and reduce the maintenance costs at the plant. These are: a) replacing the existing secondary air system with secondary air nozzles and the use of more secondary air (up to 20 % of total air) in order to generate turbulence in the high intensity combustion zone where it is most needed and b) introducing a baffle into the main stream inside the radiation shaft in order to lower the gas temperatures entering the precipitator and to remove the existing recirculation zone in the shaft.

The response of the lux-biosensors to a range of environmental pollutants was determined, as well as the stability of the biosensors to a range of environmental parameters. The biosensors were found sensitive to a range of pollutants at environmentally relevant concentrations. These included the pollutants prevailing at the contaminated site (BTEX and major co-contaminants). Analysing the bioluminescence dose-response curves to different pollutants, it was observed that the shape of the response appeared to be indicative of the nature of the contaminant present. The application of the lux-biosensors in the screening of groundwater and sediment samples from the contaminated site, showed different levels of toxicity which correlated well with chemical analysis. The sample screening produced a toxicity map of the site, facilitating the identification of hot-spot areas that could be further investigated. Samples with high levels of toxicity were serial diluted and dose-response curves determined to increasing concentrations of the toxic sample, in site uncontaminated groundwater. The shape of the dose-response curve was indicative of the nature of the main pollutant present. The toxic effect of a pollutant detected by the biosensors in spiked environmental samples (groundwater from the study site) correlated with the effect of the same pollutant on mineralisation. This allowed subsequent use of biosensor toxicity for predictive assessment of degradation potential in the presence of the pollutant tested, validating the use of the lux bioassay as a management tool for bioremediation. The bioremediation of the major contaminants (BTEX) on site can be constrained by the presence of co-contaminants or adverse environmental conditions that inhibit microbial activity. The determination of these constraints is crucial for the success of the bioremediation technologies. Using biosensor response linked to sample manipulations, it was possible to determine the contribution of broad classes of pollutants to the total toxicity of the samples.

No description available.

Three techniques are investigated in order to assess their applicability for use in landfill design, construction and monitoring. Firstly, an assessment is made of QA procedures during liner construction through the detailed evaluation of two case studies. Construction QA procedures on-site are compared to available guidelines. The research illustrates the requirement for standardised, regulated QA procedures on landfill sites in order to provide a recognised framework for construction control. The Moisture Condition Value Test (MCV) is evaluated for use as a method of monitoring the placement of compacted clay landfill liners. London Clay and Mercia Mudstone, collected from the QA case study sites, are tested in terms of their suitability as engineered clay liners. Although, London Clay is the most acceptable it is this material which exhibits the poorest results in the MCV testing. This is due to seepage from the apparatus at high moisture contents. The research highlights the problems with the interpretation of the protocol for the testing and the differences between the Scottish and English Road Research Laboratory guidelines (Green & Hawkins, 1987). Thirdly, two airborne remote sensing techniques (ATM and CASI) are appraised as methods of monitoring landfill gas, or possibly leachate migration, from two case study landfill sites in South West England. Vegetation stress can be linked to landfill gas migration (Flower et al., 1981) and this stress can be detected as a deviation from normal spectral reflectances in vegetation (Honer et a!., 1983a). Anomalies are identified on-site through remote sensing but they cannot be directly attributed to the landfills. This research emphasises the effects of contamination from other sources. It also requires the use of a simultaneous ground survey to collate data from boreholes with measurements of soil and vegetation types. Essentially, the QA case studies and the remote sensing show potential for future use and suggestions are made in this thesis for further research. The MCV technique provides a method for assessing the controlling parameters of compaction. With further development of aspects outlined in this investigation there is the potential for specified use of these techniques In landfill engineering and monitoring.

by Cheung Yun Hing Richard. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1981. / Bibliography: leaves 182-206.

Solidification technology can be an effective process for treating a variety of difficult to manage waste materials containing heavy metals prior to reuse or disposal. There are numerous commercial solidification techniques spanning a spectrum of technical complexity and cost. The most common methods include those based on cement or cement/pozzolanic materials. These materials, which are used in many solidification processes, make the technology appear simple and inexpensive. However, there are significant challenges to the successful application of this technique. The morphology and chemistry of the solidified waste forms are complex, specially when the waste streams used contain components other than the metals that are likely to be effectively immobilised. Also, the selection of the binder, depends upon an understanding of the chemistry of both the contaminants and the binder itself, to ensure efficient and reliable results. Nevertheless,a number of complex interactions are known to cause significant retardation on normal hydraulic reactions of cement-based materials, causing numerous and controversial problems. In recent years there has been renewed interest in elucidating the binding mechanisms responsible for the fixation of waste species. Carbonation, which is known to affect a wide range of cementitious materials, is a phenomenon observed by many scientists and has received very little attention. The aim of this work has been to investigate the effects of natural and accelerated carbonation on the development of mechanical and microstructural properties of solidified products as well as on the binding of metallic waste components. Particular emphasis was paid to examine the influence of different binders on the properties of carbonated solidified waste forms. The kinetics of the carbonation reaction was thoroughly examined, particularly when mix parameters such as binder/waste type and water content were varied. An examination of the resulting products showed that carbonated solidified waste materials had improved mechanical properties and increased metal binding capacity, when compared to specimens cured in nitrogen or normal atmospheric conditions. Microstructural analysis showed that large amounts of calcite where characteristics of carbonated samples. The increased formation of calcite as a result of carbonation appeared to be directly linked with the development of strength and enhanced metals fixation. NMR and FTIR spectroscopy indicated that carbonation has a significant influence on the hydration of waste forms by increasing the degree of polymerisation of the silicate hydration phases, with a consequent acceleration of the hydration of the cement paste. Examination by SEM analysis confirmed an acceleration of C3S hydration, typified by a de-calcified hydration rims and a matrix of dense calcite intergrowth infilling porosity. Some metals appeared to be incorporated in the silica-rich rims and others in the calcite rich matrix, suggesting precipitation of metal as both carbonates, silicates and complex double-salts. An examination of the kinetic of the carbonation reaction revealed that the reactivity of the different cements was different in the presence of carbon dioxide, and that when metal wastes were added the susceptibility of the paste to react with carbon dioxide increased. In general the results of this work indicate the potential of carbon dioxide for incorporation into the treatment of wastes during solidification. However, further work is necessary to establish the long-term performance of these carbonated waste forms as well as the behaviour of carbon dioxide upon different waste streams.

Digitized by Kansas Correctional Industries

Digitized by Kansas Correctional Industries

No description available.