Thermochemically induced transformations in Al-smectites: A Spanish natural analogue of the bentonite barrier behaviour in a radwaste disposal

The thermal effect induced by the Morrón de Mateo volcanic dome (Cabo de Gata volcanic region, Spain) on the adjacent bentonitised tuffaceous beds has been studied as a natural analogue of the thermal behaviour of the bentonite-engineered barrier of a geological radwaste repository. These bentonites consist mainly of Fe-rich smectites and were formed in equilibrium with seawater at temperatures between 75 and 95 °C, according to the δ18O and δD values. In contrast, bentonites from other localities in the region consist mainly of Al-smectites, formed in equilibrium with meteoric water below 25 °C.This investigation is focussed on the detection of the chemical differences between smectites from proximal and distal zones to the dome, as well as to test whether the temperatures calculated based on the O and H isotopic values correspond to their formation or transformation. The initial hypothesis was that the chosen smectites could be formed under marine conditions, being later transformed and isotopically re-equilibrated as a result of the intrusion. To check this hypothesis, a detailed mineralogical, chemical, geochemical and isotopic study has been performed on the smectitised tuffaceous materials and the overlaying biocalcarenites outcropping near and far from the dome.The results show that distal smectites are dioctahedral Al-smectites, similar to those from other deposits in the region, while proximal smectites are Fe- and Mg-rich smectites, showing two evolutionary trends on a Fe–Mg–Al ternary diagram. Similar features are observed when their structural formulae are plotted on the muscovite–celadonite–pyrophylite diagram. Thus, they plot in the smectite domain with interlayer charge less than 1, which is mainly due to octahedral substitution for distal smectites, while for proximal ones it is caused by both octahedral and tetrahedral substitutions. In this ternary diagram, the domains of both proximal and distal smectites are partially overlapped. The coexistence of di- and trioctahedral smectites was only detected in one proximal sample. Further, proximal biocalcarenites are enriched in Fe-rich dolomite in relation to the distal ones.The 87Sr/86Sr and δ13C values in carbonates and δD in smectites indicate equilibrium with seawater. In contrast, δ18O values of carbonates and smectites indicate that they were transformed and re-equilibrated between 40 and 90 °C, and between 55 and 66 °C, respectively, independently of their location with respect to the dome.These data suggest that the transformation of calcite into Mg–Fe-carbonates and the occurrence of Fe- and Mg-rich smectites near to the dome resulted from a chemically induced process at similar temperatures. The compositional differences among samples suggests that Fe, Mg and minor Mn were supplied by a contaminant plume originated from the dome, migrating through the sediments and becoming more diluted away from the source. The absence of a well-defined thermal gradient in the system could be due to the small size, semi-closed and shallow character of the basin, as well as to its high underlying volcanic activity.Finally, the results are discussed in terms of analogue processes that can be expected in the bentonite barrier of a radwaste geological repository.