It is a great pleasure for me to deliver the keynote address this morning, opening the 18th International Symposium on the Scientific Basis for Nuclear Waste Management. On behalf of the Atomic Energy Commission of Japan, I would like to welcome all of you, particularly those who have travelled across the ocean to attend this symposium.

Nuclides eventually escaping from nuclear waste repositories in crystalline rock will move with the seeping water in the fracture network. Most important nuclides interact physically or chemically with the rock and are expected to be considerably retarded allowing them to decay to insignificant concentrations. Velocity variations may allow some portions of the nuclides to move faster. Matrix diffusion and sorption on the surfaces of the rock are by far the most powerful retardation mechanisms and depend, in addition to the sorption and diffusion properties, directly on the magnitude of the “flow wetted surface”which is the contact surface between the mobile water carrying the nuclides and the fracture surfaces over which the nuclides diffuse into the matrix.

A number of field experiments have been performed over the last 15 years to help validate the concepts and models and to obtain data. A number of such experiments are described and discussed in relation to the above issues.

Static corrosion tests were carried out with a powdered simulated waste glass in deionized water at 90 °C under oxic and anoxic conditions, respectively. The corrosion tests under anoxic condition were performed in a globe box purged with mixed gas (N2+5%H2), where the pH and Eh of deionized water were maintained at 6.9 and −0.35 V vs.S.H.E. at 25 °C, respectively.

It was observed that there is a little difference between NL values under oxic and anoxic conditions. For soluble elements (Li, B, Na, Mo) and Ca, NL values under anoxic condition were slightly smaller than those under oxic condition. For Fe and Al, NL values under anoxic condition were slightly larger than those under oxic condition. For Si, Ce, La and Nd, there was no difference between NL values under oxic and anoxic conditions. The experimental results were analyzed on the basis of a corrosion model (Diffusion-combined Model), in which the solution concentration of elements associated with solution pH and Eh can be derived thermodynamically by use of PHREEQE. The analysis suggests that precipitating minerals controlling the solution concentrations of Fe and Ca under anoxic condition are different from those under oxic condition.

The deep underground environment that would correspond to a geological repository is a system open to fluid flow. It is therefore necessary to investigate the effects of solution renewal on the long-term behavior of glass in contact with water. These effects can now be simulated using the new version of the geochemical Kindis model (thermodynamic and kinetic model).We tested the model at 90°C with an SAIV ratio of 400 m−1 at twelve renewal rates of pure water ranging from 200 to 0 vol% per day. With renewal rates between 200 and 0.065 vol% per day, steady-state conditions were obtained in the reaction system: i.e. the glass corrosion rate remained constant as did the concentrations of the dissolved species in solution (although at different values depending on the renewal rate). The ionic strength never exceeded 1 (the validity limit for the Debye-Huckel law) and long term predictions of the dissolved glass mass, the solution composition and the potential secondary mineral sequence are possible. For simulated renewal rates of less than 0.065 vol% per day (27 vol% per year), the ionic strength rose above 1 (as in a closed system) before steady-state conditions were reached, making it critical to calculate long-term rates; A constant and empirical long-term rate, derived from laboratory measurement, have to be extrapolated. These calculations were based on a first order equation to describe the glass dissolution kinetics. The results obtained with the KINDIS code show discrepancies with some major experimental kinetic data (the long term rate must decrease with the « glass-water » reaction progress, under silica saturation conditions). This clearly indicates that a more refine kinetic relation is needed for the glass matrix.

The objective of this investigation is to describe the extent to which Np, Pu, Am and Tc are mobilized from vitrified high-level radioactive waste into the near field of an HLW repository in a salt formation, when a hot and concentrated salt solution comes into contact with the glass. Waste form corrosion studies are conducted with a salt solution representing the composition of a fluid phase encountered in drill holes in the Gorleben salt dome. Test temperatures are determined by the designed maximum surface temperature of 200°C for the vitrified waste in the Gorleben salt. The following results were obtained: 1. pH changes of the radio-active leachate are the same as in inactive leachates. 2. The time and temperature dependence of the reaction for the radioactive glass are in excellent agreement with that of the inactive glass. 3. Np, Pu, Am, and Tc have not been reimmobilized in secondary minerals. Hence, mobilization of these radionuclides is governed by the kinetics of glass dissolution. Pu oxidation states were analyzed and related to Pu concentrations.

Formations and durabilities of hydrated layers were compared between a soda-aluminosilicate (NAS), a soda-lime-aluminosilicate(NCAS) and a soda-lime-alumino-borosilicate(NCABS) glasses. The first step of our study was to prepare the optically transparent hydrated layers on the surface of specimens by an autoclave(400 °C, 20 kgf/cm2) treatment. Distributions of OH groups in hydrated layers were analyzed by an etch sectioning and FTIR measurement. The rates of hydration of the glasses were in the order NAS»NCAS>NCABS. The hydration of the NCABS glass, which is a modified nuclear waste glass, required the treatment longer than those of the NAS and NCAS glasses. In the second step, we investigated the durabilities of hydrated layers by immersing the specimens into a distilled water at 100 °C. The dissolutions of hydrated layers were confirmed for each glass. The dissolution rates of hydrated layers were in the order NCAS>NCABS»NAS. It has become apparent by an XPS analysis that the highest durability of the hydrated NAS glass was due to the formation of a sodium free Al2O3-SiO2 layer on the surface. The hydrated layer of the NCAS glass, while the sodium ions were almost leached out during immersion, dissolved to water most quickly than those of other glasses. In the hydrated layer of the NCABS glass, a half amount of sodium and boron ions remained and inhibited the dissolution of hydrated layer.

This paper presents the results of analyses and measurements performed on an active glass sample taken from the French vitrification facility R7.

The present work described the effects of media, such as tuff, zeolite, bentonite and Fe2O3, on the glass surface leached in deionized water or in underground water. Element depletion or enrichment differ in different media system. No crystals were found in the leached glass surfaces layer. But there are pitting corrosion and precipitates on the leached glass surfaces. The amounts, both of them, increase along with the leaching time.

Durability of simulated high-level waste glass in continuously-flowing J-13 tuff groundwater has been examined at 90°C under gamma-irradiation. The results obtained are compared with those without gamma-irradiation. The effects of groundwater radiolysis on the glass durability are discussed based on the Eh-pH excursion obtained in the present system. It is found that the groundwater tends to be reduced under gamma-irradiat ion, however, this may not influence the solubility of multivalent cations leached from the glass.

At present Na-Al-P-glass is used in Russia as matrix for high level nuclear waste which include a sufficient portion of 90Sr and 137Cs isotopes. It has been known that this type of glass is characterized by relatively poor hydrothermal stability above 120°C (Krilova et al., 1990 [1], Balukova et al., 1987 [2]). Although careful studies were devoted to the glass, some questions of geochemical behavior of Sr and Cs in the limits of the nearest repository environment have remained undecided. For example, these have been left uncertain: the mechanism of the glass leaching, phenomena limiting the glass dissolution, the detailed composition of newly formed phases, temperature dependence of the glass solubility. The main purpose of the present experimental investigation was to detect factors controlling Sr and Cs concentrations of aquous solutions and to study the possibility of new solid phase formation as a factor slowing down migration of Cs and Sr in water satureted circumstance.

Possibility of highly waste loaded borosilicate glasses up to 65wt% were investigated for HLW. In the case the waste was loaded at a content higher than 45wt%, apatite crystal was identified in the glasses. Adding above 2.5wt% of M0O3, yellow phase was observed in the 45wt% waste glass. In the case the composition of actual waste was simulated, waste(25–45wt%) glasses were characterized. Chemical durability of 45wt% waste glass was equivalent to that of 25wt% waste glass under the condition of Na20 content lower than 12wt%. Rheological behavior of 45wt% waste glass was equivalent to that of 25wt% waste glass in the range of melting temperature. Electrical resistivity of 45wt% waste glass were a little lower than that of 25wt% waste glass and it depended on the noble metal content. The Time-Temperature-Transformation (T-T-T) diagram and the leach rate of heat treated glass indicated a good thermal stability of highly waste loaded glass below the glass transition temperature. Possibility of high waste loading up to 45wt% was elucidated.

Hydrated glass was prepared by the treatment in an autoclave. Specimen in a good state was obtained under unsaturated water vapor pressure conditions. The obtained glass has an silica-rich hydrated layer and proved to be more durable than the original glass. There are some kinds of hydroxyl species in the hydrated glass and there are some patterns in the depth profile of water, indicating that the rate-controlling process is not a simple diffusion and the hydration process is a complicated reaction depending on the conditions. Water in hydrated glass is tightly bonded and a disintegration of hydrated glass in this study occurs at more than 560°C.

To immobilize a high sulfate radioactive wastes a system Na2O-A12O3-P2O5-SO3 has been chosen as one where glasses have a relatively low melting points and good chemical durability. Glasses within partial system 44 Na2O, 20 A12O3 (36-x) P2O5 x SO3 have been prepared at 1000 °C. A possibility of assimilation up to 12 mole % of SO3 has been established. The basic properties of sulfate-containing glasses as density, microhardness, thermal expansion coefficient, transformation and deformation temperatures, viscosity, electric resistivity, leach rate of ions and diffusion coefficients of 22Na, 35S, 90Sr and 137Cs have been measured. Glass structure by infrared and EPR spectroscopies has been investigated.

Models have been developed to calculate the density, molten-state viscosity and initial corrosion rate according to the chemical composition of glass formulations used to vitrify high-level fission product solutions from reprocessed light water reactor fuel. Developed from other published work, these models have been adapted to allow for the effects of platinoid (Ru, Pd, Rh) inclusions on the molten glass rheology.

This paper presents a review of the principles underlying a continuum formulation of reactive transport in a porous medium. Partial differential equations representing conservation of mass are derived for transport by advection, diffusion, and electrochemical migration combined with chemical reaction of aqueous species and solids. Several examples are presented to illustrate the general theory. These include weathering along a narrow crevice, electrochemical migration in a dilute NaCl solution, secondary pyrite formation mediated through intermediate sulfur oxidation states, and a description of a uranium roll-front deposit. Numerical techniques which take advantage of the quasi-stationary state approximation, based on the much longer time scale involved in mineral alteration compared to that characterizing changes in the aqueous phase, permit solving the reactive transport equations over geologic time scales.

We consider some reactive geochemical transport problems in groundwater systems. When incoming fluid is in disequilibrium with the mineralogy sharp transition fronts may develop. We show that this is a generic property for a class of systems where the timescales associated with reaction and diffusion phenomena are much shorter than those associated with advective transport. Such multiple timescale problems are relevant to a variety of processes in natural systems: mathematically methods of singular perturbation theory reduce the dimension of the problems to be solved locally. Furthermore we consider how spatial heterogeneous mineralogy can impact upon the propagation of sharp geochemical fronts.

We develop an asymptotic approach in which we solve equations for the evolving geometry of the front and indicate how the non-smooth perturbations due to natural heterogeneity of the mineralogy on underlying ground water flow field are balanced against the smoothing effect of diffusion/dispersive processes. Fronts are curvature damped, and the results here indicate the generic nature of separate front propagation within both model (idealized) and natural (heterogeneous) geochemical systems.

Transfer factors of iodine from soil to rice were obtained by laboratory experiments using 125I tracer. Two typical soil types in Japan, Andosol and Gray lowland soil, were used. The transfer factor (TF) is defined as ’concentration of the nuclide in a plant organ at harvest’ divided by ’concentration of the nuclide in dry soil’. The TFs for brown (hulled) rice were 0.006 for Andosol and 0.002 for Gray lowland soil. The TFs for different organs of rice plants decreased in the order of blade > stem > rachis > unhulled rice >> brown rice.

The concentration of iodine in soil solution under flooded conditions varied with time during cultivation. The iodine concentration in rice plants seemed to be influenced by the soil solution.

The effect of removal of 1–129 from paddy fields by harvesting rice plants was also modelled. Even assuming continuous deposition of 1–129 onto the field, annual harvesting of the blades and stems of rice plants could effectively reduce the amount of the nuclide in the root zone.

Current concepts of the geological disposal of low- and intermediate-level radioactive wastes in the UK envisage the construction of a mined facility (incorporating cementitious engineered barriers) in chlorite-bearing rocks. To model accurately the fluid-rock reactions within the ‘disturbed zone’ surrounding a repository requires functions that describe mineral dissolution kinetics under pH conditions that vary from near neutral to highly alkaline.

Therefore, an experimental study to determine the dissolution rates of Fe-rich chlorite has been undertaken as part of the Nirex Safety Assessment Research Programme. Four experiments have been carried out at 25 °C and four at 70 °C, both sets using a range of NaCl/NaOH solutions of differing pH (of nominal pH 9.0,10.3, 11.6 and 13.0 [at 25 °C]).

Dissolution rates have been calculated and were found to increase with increasing pH and temperature. However, increased pH resulted in non-stoichiometric dissolution possibly due to preferential dissolution of part of the chlorite structure relative to another, or reprecipitation of some elements as thin hydroxide or oxyhydroxide surface coatings on the chlorite.

These results also show that chlorite dissolution is appreciably slower than that of albite and quartz at both 25 and 70 °C, but slightly faster than that of muscovite at 70 °C.

Diffusion of a charged colloidal particle in a two-dimensional simple shear flow was studied by means of Monte Carlo calculations and the effects of a bounding wall and charge of a particle on convective diffusion were elucidated. Taking charge effects into account has a marked effect on the diffusion behavior of the particle, increasing the migration distance. Diffusion of latex colloidal particles in a quartz-powder packed cell was also studied by through-diffusion methods. For the large latex colloidal particles, the effective diffusion coefficients measured are larger than those estimated by Stokes-Einstein equation.

AECL Research is developing a concept for the permanent disposal of nuclear fuel waste. A program to address the potential effects of microbial action on the integrity of the multiple barrier system, on which the disposal concept is based has been initiated. This microbial program focusses on answering specific questions in areas such as the survival and growth of microbes in compacted clay buffer materials and the potential consequences for container corrosion and microbial gas production; microbial effects on transport of radionuclides through the buffer into the geosphere; the presence and activity of microbes in deep granitic groundwaters; and the effects of biofilms on radionuclide migration in the geosphere.