Bentonites are candidate materials for encapsulating radioactive waste within barrier systems in crystalline rocks. In the ‘Alternative Buffer Material’ (ABM) test in the hard rock laboratory in Äspö, Sweden, six packages of eleven different buffer materials (mainly bentonites) with various exchangeable cation populations were packed vertically with an iron tube used as a heater in the center. After installation, the second ‘ABM package’ (ABM-II) was first allowed to saturate with water for approximately 2.5 years. The blocks were then exposed to a temperature of up to 141°C for approximately 3–4 years. The hypotheses for the present study were: (1) no horizontal gradient of the cation exchange population was present in the individual blocks of ABM-II because ABM-II had a longer reaction time in comparison to the ABM-I package, which did not have horizontal gradients; (2) the exchangeable cation Ca2+:Na+:Mg2+ ratio was equal in all blocks of ABM-II and was independent of block position in the package. As expected from ABM-I, all blocks in the ABM-II experiment showed large differences between the measured values of the reference materials and the reacted samples. The exchangeable Na+ and Mg2+ values in ABM-II were reduced by up to 55% to 59% in comparison to the reference material. Contrary to the first hypothesis, horizontal gradients were observed in ABM-II; and, contrary to the second hypothesis, the exchangeable cation ratios differed markedly in the different reacted buffer materials. The largest total Na+ loss was observed in the middle part (-67%), whereas Mg2+ values decreased by 79% in the upper part. The exchangeable Ca2+ values increased strongly in ABM-II, particularly in the upper part. The most useful parameter to distinguish between ion exchange equilibria of ABM-I and ABM-II was the Na+/Mg2+ ratio. This ratio was constant in ABM-I (3.0) and had a similar ratio (3.5) in the lower part of ABM-II; however, the ratio strongly increased (5–10) in the upper part of the ABM-II package. The large Na+/Mg2+ ratios in the upper part of ABM-II could possibly be explained by water loss into the rock (caused by a pressure drop and boiling) and subsequent water uptake.

Bentonites are candidate materials for high-level radioactive waste (HLRW) repositories and, therefore, are investigated with respect to long-term stability. In order to identify possible bentonite alteration processes, long-term in situ tests are conducted in rock laboratories. The prototype repository in situ experiment (PR) is one of the best examples of this kind of test due to the size of the installation as well as the duration. In the present study, chemical and mineralogical alteration processes of the bentonite MX 80 after an 8 y heating period were investigated. The water content of all samples increased following inflowing Na-Ca-Cl-type granitic groundwater causing cation exchange in the bentonite buffer materials. Exchangeable magnesium was desorbed in the buffer and MgO concentration increased at the bentonite-Cu canister interface; the Mg sink could not be detected, however. CaO also accumulated at this interface mainly as Ca carbonate and Ca sulfate. Cu corrosion products were identified at the bentonite-canister interface by chemical analysis, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDX), and differential thermal analysis. Up to 0.5 mm into the bentonites Cu could be detected by SEM-EDX. No cristobalite dissolution was observed in contrast to other in situ tests in which iron heaters were used. The corrosion products and the lubricant which was added during manufacturing of the bentonite blocks were mixed with the bentonite at the bentonite-canister interface. A quantitative measure of that mixture was the decrease in the cation exchange capacity (CEC). The CEC also reduced in all other samples, however, compared to the CECs of the reference samples, particularly in the warmer deposition hole 5 compared to the colder deposition hole 6. Overall, the PR in situ experiment proved that cation exchange reactions occurred in full-scale bentonite buffer experiments in all bentonite blocks but structural degradation of smectite could not be identified.

Bentonites are candidate materials for the encapsulation of radioactive waste. In the ‘Alternative Buffer Material test’ (ABM), compacted ring-shaped blocks of eleven different buffer materials (mainly bentonites) were packed vertically on top of each other with an iron tube as heater in the centre. These buffer materials started with various exchangeable cation populations (ECpopulation). The first ‘ABM package’ was terminated 28 months after installation and the bentonites had been exposed to the maximum temperature (130°C) for about one year. The aim of the present study is first: to describe modification of the cation exchange population, and second to understand the influence of the groundwater on cation exchange at different scales. No significant horizontal variation of any exchangeable cation (EC) was detected between 1 and 7 cm distance from contact with the iron tube. Large total differences of the ECpopulations, however, were observed for the individual blocks after the field experiment (n = 21 blocks) with respect to the composition of the reference materials. The average cation exchange capacity (CEC) values of the analysed bentonites (n = 9 blocks) decreased by 5.5 meq/100 (1.1 – 8.8 meq/100 g) after the experiment. Exchangeable Na+ and Mg2+ decreased on average, whereas Ca2+ increased. This trend was pronounced in the top region of the parcel (upper seven blocks). Although most changes occurred on the large scale of the whole test parcel, small but important changes were also recorded in the vertical direction on the centimetre scale. The observed differences cannot be explained assuming simply that a bentonite reacts only with neighbouring blocks, which would mean that the system was more or less closed. The differences are much larger and the only conclusion from this observation is that the whole package seems to be influenced by the groundwater which was added from a water tank at the experiment site, enabling at least partial equilibration between the different blocks.