In situ investigations and reactive transport modelling of cement paste/argillite interactions in a saturated context and outside an excavated disturbed zone

The interactions between cementitious materials and a clayey deep formation were investigated by studying the specific in situ context of the Tournemire Underground Research Laboratory (URL) of the French Institute for Radioprotection and Nuclear Safety and by reactive transport modelling using the HYTEC code. The study forms part of the safety assessment framework for the deep geological disposal of high to intermediate level long-lived radioactive waste. The in situ context investigated in the Tournemire URL corresponds to an engineered cemented borehole crosscutting the Toarcian argillite formation. The argillite/CEM II cement paste contacts have been in place over 18 a and were sampled in a saturated context outside the excavated disturbed zone (EDZ). Studies of the mineralogy (XRD, carbonatometry, SEM and TEM), petrophysical properties (BET) and geochemistry (TOC, Sr contents, C, O and Sr isotopes, EDS analyses) were carried out both on the argillite and on the cement paste in contact. Alteration of the cement paste is clearly expressed by decalcification and the opening of macroporosity. These modifications are mainly due to the dissolution of portlandite. The neoformation of C-S-H phases was identified in the first few micrometre next to the argillite interface, along with secondary carbonates at the outermost contact. Geochemical measurements argue for the introduction of a sedimentary fluid into the macroporosity of the cement paste to explain the formation of part of these secondary phases. This hypothesis is considered and tested using the HYTEC code, which indicates that such transport could have occurred near the argillite/cement paste contact at a very early stage. After this stage, the transport was reversed and 'cementitious' fluids flowed from the cement paste to the argillite. The changes brought about by these fluids are observed over a thickness of 11-13 mm in a so-called 'black rim', in which carbonates and C-S-H secondary phases are identified in the matrix of the sediment. An illitization process may also be observed in this altered rim, reaching its maximum development towards the inner part. Geochemical analyses show that the argillite disturbances are strictly confined to the black rim. Theoretical mineralogical profiles based on thermodynamic equilibria defined by the HYTEC code are in good agreement with the observations, and are used to achieve a better understanding of transport processes. (c) 2013 Elsevier Ltd. All rights reserved.