Tracing interactions between natural argillites and hyper-alkaline fluids from engineered cement paste and concrete: Chemical and isotopic monitoring of a 15-years old deep-disposal analogue

Applied geochemistry / Volume 27, numéro 7, juillet 2012, pages 1384-1402

Samples of Toarcian argillite were collected both next to and far from a CEM II cement paste and a CEM II concrete, within the specific context of a 15-a old borehole located in the Tournemire Experimental Platform (Aveyron, France). The objectives were evaluation of the mineralogical and geochemical changes of the claystone at the contact with the cementitious materials and determination of the spatial extent of the interactions. The approach includes the examination of the mineralogical (XRD, SEM, TEM), chemical (major, trace, rare earth elements) and isotopic (Sr, C, O) compositions of argillite whole-rocks and of various soluble phases, at two scales: in the rock matrix (P1 scale) and along micro-cracks (P2 scale). The two study scales outline nearly similar mineralogical modifications, shown by the presence of Ca silicate hydrates (C–S–H) and newly-formed CaCO₃ within 10–15 mm of the cement paste and concrete. Chemical data from whole-rock argillites indicate few changes in a slightly thicker zone (18–20 mm), mainly consisting of an increase in the CaO wt.%, and a decrease in Sr contents. The other elementary contents remained quite constant except for MgO, which suggests redistribution with precipitation of a Mg-rich mineral phase at 20 mm from cement paste/concrete interface. Acetic acid leachates had more pronounced variations, including a decrease of the total elementary content in the same ‘geochemical disturbed zone’ (GDZ), together with a significant increase of the Sr isotopic ratios. A combination of Sr and C/O isotopic patterns was used to distinguish the behavior of secondary cementitious phases in the clay-rich rock: (i) calcite dissolution and re-precipitation is supported by C/O isotopic data and (ii) C–S–H neoformation is evidenced by the ⁸⁷Sr/⁸⁶Sr ratios; this tool also contributes to determine the origin of the fluids. The proportion of newly-formed C–S–H in the matrix and in the micro-cracks of the argillite is modeled.