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The ability of zeolites, particularly clinoptilolite, to immobilise Cs arising as an intermediate level radioactive waste is studied. The zeolites are incorporated into Portland cement blends containing additives such as blast furnace slag, pulverised fuel ash and silica fume, and high alumina cement blends. Desorption of Cs+ from the zeolite by ion-exchange cement pore fluid species, mainly K+, Na+ and Ca is studied and ion-exchange isotherms are presented. The Cs distribution between clinoptilolite and cement pore fluid is studied by X-ray diffractometry (XRD) and by chemical analysis of the pore fluid. Some Cs is released into the pore fluid, mainly by ion-exchange with K. The kinetics and mechanism of the pozzolanic reaction between clinoptilolite and Portland cement is studied at various temperatures, using a selective dissolution method, as well as XRD, thermogravimetric analysis and analytical electron microscopy. A model is developed, whereby long-term predictions of clinoptilolite reactivity can be made. Methods of limiting the pozzolanic reaction to ensure the long-term persistence of clinoptilolite in cement by blending are investigated. Slag cements show lowest reactivity. Leach tests are carried out on cement-clinoptilolite cylinders (45x80mm) using a standard leaching method. These confirm the importance of ion-exchange and chemical reactivity in determining leach rate. Additionally, the effect of factors such as clinoptilolite particle size, Cs -loading level, clinoptilolite-cement ratio, quantity and type of cement additive, curing temperature, curing time, leaching temperature and mercury porosity on leach rate are investigated. An optimal cement-clinoptilolite blend is suggested. A method is described for the measurement of oxidation-reduction potential (Eh) of cement pore fluids extracted under pressure, and of measuring the poising capacity of solid and aqueous phases. OPC is mildly oxidising, whereas slag cements provide a reducing environment due to the presence of S-containing species. The implications of E. and pH in terms of radwaste immobilisation are discussed.

The calculation of dry particle deposition velocity (Vg) for small particles in field studies is subject to much variability between theoretical and measured values. This work will assess some of the factors which may influence the calculation of Vg. The other key parameter which is used to define the near-surface exchange of material is the resuspension factor (K). The certainty of using a Vg which is representative of small particles typically 1 pm requires clarification. During September 1993-1994, four size-selective air and deposition experiments were carried out at an on-site and off-site sampling location close to the BNFL Sellafield nuclear reprocessing plant in Cumbria UK. Dry and total (wet & dry) particle deposition velocities were determined for ^^^Cs, The dry deposition velocities of naturally-occurring ^Be were also determined and used as a 'marker' for small particle transport processes. Resuspension factors K (m ^) for radiocaesium and Plutonium were also derived. Automated individual particle characterisation (AlP) using scanning electron microscopy coupled to energy-dispersive x-ray analysis (SEM-EDXA) was used to determine the particle size distribution and associated elemental composition of material deposited to Frisbee deposition collectors. Enhanced a-emitting hot-spots from surface soils and material deposited to Frisbee collectors at 1 m above ground level were isolated and characterised for size and shape using nuclear track detector film, LR-115. Dry particle deposition velocities for ^^^Cs, 239+240py and were commonly in excess of 1E-03 m s"^ by more than two orders of magnitude. Total deposition velocities (dry and wet) were even higher with values ranging from 0.2 m s^ -1 ms"^ for both radiocaesium and plutonium. High derived values of dry deposition velocity for radiocaesium and plutonium were to some extent influenced by air sampling artefacts. Air sampling artefacts result in an under-estimation of airborne activity for radioactivity associated with particle diameters >10 pm. The derived values of dry particle deposition velocity for ^Be were consistent with literature values of sub-micron sized particles with evidence of a seasonal spring maximum. Resuspension factors K (m'^) for radiocaesium and plutonium agreed well with literature values of weathered weapons fallout values which ranged from 2E-08 to 5E-11 (m"^) for plutonium and radiocaesium respectively. Differences in dry particle deposition velocities for radiocaesium and plutonium between the on-site and off-site locations varied by no more than a factor of three. Correlations between dry particle deposition velocities for Cs and Pu with wind speed, wind direction and precipitation rates were not found. Size-specific air sampling show that the majority of the plutonium was predominantly associated with the >11 lam aerosol size fraction. The association between activity and large particle size suggest this material was probably attached to large soil-derived particles. Plutonium isotope data indicate this material originated fromthe nuclear weapons programme of the late 1950's-earty 1970's. Radiocaesiumactivities were equally distributed between the < 10 ixm and > 11 ^m aerosol fractions for two out of the four runs. This suggests that historically deposited ''^^Cs and current emissions contributed to measured airborne activities. Enhanced a-emitting hot-spots were isolated from bulk surface soils and in material deposited to Frisbee collectors. Rare particles such as these with atypical activities of Pu may lead to mis-leadingly high deposition fluxes. The calculation of Vg in the field is therefore sensitive to the presence of these particles because they are not representative of the aerosol flux and their size s 50 |im precludes their collection by the Pmio air sampler. The main conclusions of this work indicates the very high values of Vg sometimes measured in the field are strongly influenced by large resuspended soil particles and associated air sampling artefacts. The inclusion of large particles within the deposition flux is confirmed by size selective mass based Vg using scanning electron microscopy

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The mechanisms controlling radiocaesium migration through the peat soil were investigated by considering physico-chemical & biological factors affecting radionuclide adsorption/desorption in the peat soil using the Batch & Column Methods as well as a "Direct Fumigation Extraction Method". The biological factors were investigated under different conditions by variation of the micro-organisms content in the peat soil, the soil solution and leaching conditions. Samples of peat soil were reacted with solutions containing caesium ions, and the effect on caesium-K_d determined. The caesium adsorption/desorption was found to be influenced by concentration of caesium and other cations (NH₄⁺, K⁺ and Ca⁺⁺) and by the pH of the solution. Below pH 3, in presence of calcium and potassium, desorption could occur as the exchangeable sites on microparticles were replaced by other cations. At pH>1, in presence of ammonium, adsorption could occur. The distribution coefficient, K_d value was strongly reduced following the addition of NH₄⁺, K⁺ and Ca⁺⁺ at a fixed pH. NH₄⁺ was found to be more effective in the caesium desorption than the other cations. By increasing the concentration of radiocaesium (>0.2 MBq/100μl) the effect became much less leading eventually to an increase in caesium-K_d values. A decrease in the caesium-K_d was also observed at pH<3 in peat samples. It was found that the caesium adsorption approached to an equilibrium state at pH>3 depending upon caesium concentration in peat solution. Caesium adsorption took 180 days to reach equilibrium state. For the measurement of the release/uptake of radionuclides in the peat soils by the microbial biomass, homogenised wet peat samples were fumigated by chloroform. The influence of the microbial population present in the peat on the environmental mobility of caesium was clearly demonstrated.