A database of dissolution and precipitation rates for clay-rocks minerals Nicolas C.M. Marty a,⇑ , Francis Claret a , Arnault Lassin a , Joachim Tremosa a , Philippe Blanc a , Benoit Madé b , Eric Giffaut b , Benoit Cochepin b , Christophe Tournassat a a BRGM, 3 Avenue Claude Guillemin, 45060 Orléans, France b ANDRA, 1/7 Rue Jean Monnet, 92298 Châtenay-Malabry, France article info Article history: Available online 20 October 2014 abstract Many geoscientific fields use reactive transport codes to set up and interpret experiments as well as to understand natural processes. Reactive transport codes are also useful to give insights in the long term evolution of systems such as radioactive waste repositories or CO 2 storage sites, for which experiments cannot reach the targeted time scale nor the dimension of those systems. The consideration of kinetic reaction rates is often required to reproduce correctly the geochemical and transport processes of inter- est. However, kinetic data are scattered in the literature, making data and selection a tedious task. Kinetic parameters on a single system are also highly variable depending on data choice, interpretation and cho- sen kinetic modelling approaches, thus making inter-comparison of modelling studies difficult. The pres- ent work aims at proposing a compilation of kinetic parameters to overcome part of above cited problems. The proposed selection was done (i) to ensure consistency of data selection criteria and data treatment and (ii) to ease the use of common kinetic parameters that are independent of the chosen geo- chemical modelling code. For those two reasons, the kinetic formalism of the transition state theory (TST) was chosen. The selection of minerals is currently limited to those present in clay rich rocks and cements, reflecting the effort made at predicting the evolution of radioactive waste underground storage systems. Still, the proposed compilation should also be useful for other applications such as CO 2 sequestration. Ó 2014 Elsevier Ltd. All rights reserved. 1. Introduction Over the past fifty years, numerical simulations have increas- ingly been used in geochemical studies. They are used to set up and interpret experiments, to understand natural processes (e.g. Appelo et al., 1998; Mayer et al., 2002; Soler, 2003; Steefel et al., 2005; Steefel and Lichtner, 1998; Steefel and MacQuarrie, 1996), and to predict the long-term behaviour of systems such as radioac- tive waste repositories (e.g. De Windt et al., 2008; Gaucher et al., 2004; Kosakowski et al., 2009; Kulik et al., 2013; Lu et al., 2011; Marty et al., 2010; Savage et al., 2002, 2010; Shao et al., 2009) or CO 2 storage sites (e.g. Gherardi et al., 2012; Hellevang et al., 2013; Kang et al., 2010; Pruess et al., 2004; Trémosa et al., 2014). Reactive transport codes enable us to predict the geochemical behaviour over time scales that cannot be experimentally repro- duced and/or for spatial dimensions that cannot be instrumented. Reactive transport models often need to consider reaction rates in order to represent out-of-equilibrium geochemical processes that occur in laboratory or natural environments (e.g. Appelo et al., 1998; Hellevang et al., 2013; Marty et al., 2010; Trémosa et al., 2014). Amongst existing models, the most popular must be the kinetic model based on the transition state theory (TST model) as described by Lasaga (1981). Other mechanistic models exist, such as ones based on activated surface complexes (Oelkers, 2001), the stepwave model (Lasaga and Luttge, 2001), and the nucleation theory (Dove et al., 2005). However, these formalisms which should be considered for their implementation in geochemical codes are complex and are often applicable to only the simplest cases (e.g. a single mineral phase) due their high computation cost. The use of kinetics in numerical models is facing several chal- lenges. One of the difficulties comes from the representation of incongruent dissolution processes that have been reported for some minerals (Bickmore et al., 2001; Golubev et al., 2006; Kaviratna and Pinnavaia, 1994; Marty et al., 2011). In addition, the numerical representation of the evolution of surface roughness and area during the reaction is very uncertain. Several models cal- culate the evolution of the reactive surface area as a function of changes in the mineral reaction progress (Cochepin et al., 2008; Emmanuel and Berkowitz, 2005; Lichtner et al., 1996; Noiriel et al., 2009). Moreover, laboratory experimental rates and those http://dx.doi.org/10.1016/j.apgeochem.2014.10.012 0883-2927/Ó 2014 Elsevier Ltd. All rights reserved. ⇑ Corresponding author at: BRGM, D3E/SVP, 3 Avenue Claude Guillemin, F-45060 Orléans, Cedex 2, France. Tel.: +33 2 38 64 33 43; fax: +33 2 38 64 30 62. E-mail address: n.marty@brgm.fr (N.C.M. Marty). Applied Geochemistry 55 (2015) 108–118 Contents lists available at ScienceDirect Applied Geochemistry journal homepage: www.elsevier.com/locate/apgeochem