Chemical durability of fully radioactive, high-sodium borosilicate glass K-26 was evaluated using the product consistency test PCT-A. Examination revealed normalised leaching rates as high as 5.93•10−2, 4.05•10−2 and 2.93•10−2 g/m2•day for sodium, boron and silicon respectively. Data on chemical durability of glass K-26 are consistent with similar composition glasses. These are of particular interest for performance assessment models.

Field experiments have run for over 14 years to evaluate the behaviour of the same high-sodium content radioactive waste borosilicate glass buried in a loamy soil (glass K-26) and in an open testing area (glass Bs-10). Processing of field data for glass Bs-10 tested in an open area has resulted in a dissolution rate r = 0.42 µm/y and caesium diffusion coefficient D ≍ 1.8 10−20 m2/s at testing temperatures up to 19 oC. Both ion-exchange and hydrolysis control the corrosion of this glass. Processing of field data for K-26 glass revealed an insignificant role of glass dissolution. The caesium diffusion coefficient was estimated as D ≍ (3.4-5.1) 10−21 m2/s. Due to the relatively low storage temperatures (4.5 oC) used the leaching behaviour of glass K-26 is believed to be controlled by ion exchange processes. This mechanism is likely to remain dominant until the decay of 137Cs in the glass is below exemption levels.

Two disparate reaction mechanisms have been invoked to explain the reactivity of glass in contact with aqueous solution. One model is based on arguments from Transition State Theory (TST), which postulates that glass dissolution rates are surface reaction controlled. Alternatively, the second model argues that release of elements from glass to solution is governed by diffusion through an altered layer that forms on the surface of glass. Vertical Scanning Interferometry (VSI) is a new technique that allows one to observe surface features of specimens exposed to solution and may, potentially, be used to distinguish between competing models. We performed a series of dissolution experiments with a suite of glass compositions from chemically simple (sodium borosilicate) to complex (sixteen component borosilicate). Dissolution rates were determined using single-pass flow-through (SPFT) apparatus at 90°C and pH = 9 and over a solution saturation interval. Upon termination of the experiments, glass coupons were examined by VSI techniques. Effluent chemistry and VSI measurements indicate a nearly constant rate of 2.2 to 3.4 g m-2 d-1 over the solution interval; rates calculated from both methods are identical within experimental uncertainty. We argue that this glass is phase separated, and propose a model for dissolution based on the relative rates of dissolution of the two glass compositions. The data are consistent with a modified version of TST and indicate the potency of VSI methods to elucidate glass reaction mechanisms.

The corrosion resistance of a series of zirconium-substituted gadolinium pyrochlore, Gd2(Ti1-x Zrx)2O7, where x = 0.0, 0.25, 0.50, 0.75, and 1.00, were evaluated using single-pass flow-through (SPFT) apparatus at 90°C and pH = 2. The zirconate end-member, Gd2Zr2O7, has a defect fluorite structure, which distinguishes it from the face-centered cubic structure of the true pyrochlore specimens. In addition to the chemical variation, the samples include annealed, un-annealed, and ion-bombarded monoliths. In the case of the titanate end-member, Gd2Ti2O7, the annealed specimen exhibited the least reactivity, followed by the un-annealed and ion-bombarded samples (2.39×10-3, 1.57×10-2, and 1.12×10-1 g m-2 d-1, respectively). With increasing zirconium content, the samples displayed less sensitivity to processing or surface modification with the zirconate end-member exhibiting no difference in reactivity between annealed, un-annealed, and ion-bombarded specimens (rate = 4.0×10-3 g m-2 d-1). In all cases, the dissolution rate decreased with increasing zirconium content to the Gd2(Ti0.25Zr0.75)2O7 composition (1.33x10-4 g m-2 d-1), but the zirconate end-member yielded rates nearly equal to that of the titanate end-member. These results demonstrate that to achieve the greatest radiation and corrosion resistance in this series, the Gd2(Ti0.25Zr0.75)2O7 composition should be considered.

The design and analysis of waste package and engineered systems for geologic disposal of radioactive wastes are being conducted in most countries with so-called performance assessment models and associated computer codes that solve the governing equations. The models range in complexity from simple 1-D analytical solutions to multidimensional, multicomponent reactive transport models implemented in large computer codes. Borosilicate waste glass is certainly the most studied and probably best understood waste form that has been developed for encapsulating high-level waste. Reasonably good models are available that describe the reaction kinetics and transformation of the glass into a paragenetic sequence of more stable secondary phases. Given the broad range of computational tools and extensive database on glass/water reactions that is available, it is surprising that little progress has been made to link these models and data in a comprehensive performance assessment of waste glass in a repository setting. In this paper, we will explore reasons why this linkage has not been developed, give several examples illustrating the importance of doing so, and illustrate an approach to accomplish such a linkage.

Hydration rind thicknesses found on obsidian artifacts provide one means of estimating the age of an archaeological site. The model used in the method usually assumes a diffusion-controlled reaction of the glass with water. However, results using this model are not always in agreement with other dating methods. Observations of secondary mineral formation on glasses in contact with water vapor suggests that other rate-controlling mechanisms may be operative. In this paper, we apply the glass dissolution code GLASSOL, coupled with the geochemical code PHREEQE to model the reaction of Glass Mountain obsidian in water. The results show the importance of accounting for the effects of solution chemistry on the time-dependence of the hydration reaction.