Definition of an equilibration protocol for batch experiments on Callovo-Oxfordian argillite

In order to elude difficulties concerning reproducing controlled conditions and avoiding chemical perturbation from sampling to laboratory experiments, an equilibration protocol of crushed Callovo-Oxfordian argillite in contact with synthetic pore water is proposed. It consists of a rinse-cycle with chosen synthetic waters. Hence, artifacts such as porosity variability, secondary paragenesis of evaporitic feature and a consecutive changing of water chemistry may be corrected. Equilibrium conditions are defined when both rinsing and leaching solutions are identical. In the first phase of this work, an input grid concerning reaction duration, number of rinsing and water/rock ratio associated to a specify methodology (anoxic and P CO 2 controlled atmosphere glove box) are given. We propose a water/rock ratio equal to 5, a first 72 h rinse followed by three others of 24 h. The protocol was tested among nine synthetic waters and validated regarding major aqueous elements. A geochemical modelling allowed us to identify the reactional mechanisms occurring during the whole procedure in terms of (1) modelling reactions taking place during the various rinses; (2) quantification of the dissolution/precipitation reactions and (3) modelling the condition of the sample. According to the rinsing water composition and P CO 2 , dissolution of carbonate minerals may occur and is accompanied by a redistribution of sorbed species at argillaceous mineral surface. Solution analysis coupled with geochemical modelling show an increasing of aqueous K +, consequent upon cationic exchange reactions K +/Na +. Besides, the dissolution of carbonate minerals produced Ca 2+ and Mg 2+ which in turn are exchanged with K + and H +. Silica is controlled by the solubility of chalcedony. However, pH seems to be hardly imposed from the rinsing solution, since it is principally buffered by calco-magnesio-carbonate system. Moreover, anoxic conditions are not sufficient to restore natural reducing conditions. Redox potentials measured are all in the region of 200 mV/ESH. There is every indication that such values are either potential out of equilibrium or values imposed by pyrite oxidation products. At least, high increases of cations, SO 4 2− and in a less extent Cl − contents show typically the dissolution of evaporitic minerals formed by desiccation and inherited from samples storage historic. However, it is not out of the question that reducing potentials are thought to be expected if samples