No description available.

No description available.

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 International Commission on Radiological Protection (ICRP) has modeled twelve reference animal and plant (RAP) species using simple geometric shapes in Monte���Carlo (MCNP) based simulations. The focus has now shifted to creating voxel phantoms of each RAP to advance the understanding of radiation interactions in nonhuman biota. The work contained herein presents results for the voxel phantom of the Dungeness crab, Metacarcinus magister, the Sand Dab, Limanda limanda, and the brown seaweed, Fucus vesiculosus, and details a generalized framework for creating voxel phantoms of the other RAPs. Absorbed fractions (AFs) for all identified organs were calculated at several discrete initial energies: 0.01, 0.015, 0.02, 0.03, 0.05, 0.1, 0.2, 0.5, 1.0, 1.5, 2.0, and 4.0 MeV for photons and 0.1, 0.2, 0.4, 0.5, 0.7, 1.0, 1.5, 2.0 and 4.0 MeV for electrons. AFs were then tabulated for each organ as a source and target at each energy listed above. AFs whose error exceeded 5% are marked with an underline in the data tables; AFs whose error was higher than 10% are shown in the tabulated data as a dashed line. The AF���s were highly dependent on organ mass and geometry. For photons above 0.5 MeV and electrons above 0.2-0.4 MeV a nontrivial amount of energy escapes the source organ. / Graduation date: 2013

Thesis (Ph. D.)--Lehigh University, 2002. / Includes vita. Includes bibliographical references (leaves 128-134).

published_or_final_version / abstract / toc / Physics / Doctoral / Doctor of Philosophy

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

No description available.

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.

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.