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Journal Articles Geochimica et Cosmochimica Acta Year : 2009

A robust model for pore-water chemistry of clayrock


The chemistry of pore water is an important property of clayrocks being considered as host rocks for long-term storage of radioactive waste. It may be difficult, if not impossible, to obtain water samples for chemical analysis from such rocks because of their low hydraulic conductivity. This paper presents an approach for calculating the pore-water compositions of clayrocks from laboratory-measured properties of core samples, including their leachable Cl and SO4 concentrations and analysed exchangeable cations, and from mineral and cation exchange equilibria based on the formation mineralogy. New core sampling and analysis procedures are presented that reduce or quantify side reactions such as sample oxidation (e.g. pyrite) and soluble mineral dissolution (celestite, SrSO4) that affect measured SO4 concentrations and exchangeable cation distributions. The model considers phase equilibria only with minerals that are observed in the formation including the principal clay phases. The model has been used to calculate the composition of mobile pore water in the Callovo-Oxfordian clayrock and validated against measurements of water chemistry made in an underground research laboratory in that formation. The model reproduces the measured, in situ pore-water composition without any estimated parameters. All required parameters can be obtained from core sample analysis. We highlight the need to consider only those mineral phases which can be shown to be in equilibrium with contacting pore water. The consequence of this is that some conceptual models available in the literature appear not to be appropriate for modelling clayrocks, particularly those considering high temperature and/or high pressure detrital phases as chemical buffers of pore water. The robustness of our model with respect to uncertainties in the log K values of clay phases is also demonstrated. Large uncertainties in log K values for clay minerals have relatively small effects on modelled pore-water compositions.


Earth Sciences

Dates and versions

hal-00512606 , version 1 (31-08-2010)



Eric C. Gaucher, Christophe Tournassat, F.J. Pearson, Philippe Blanc, Catherine Crouzet, et al.. A robust model for pore-water chemistry of clayrock. Geochimica et Cosmochimica Acta, 2009, 73 (21), p.6470-6483. ⟨10.1016/j.gca.2009.07.021⟩. ⟨hal-00512606⟩


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