This paper presents an extension of the application field of PHREEQC geochemical software for modelling the dynamic leaching tests (and scenarios) by taking into account the leachant compartment as complex reactive/transport system and the coupling of many reactive compartments linked by substance fluxes. This study focuses on the specific case of dynamic leaching of monolithic porous materials (particularly the case of continuous monolithic leaching test. CMLT) where reaction/diffusion occurs in the porous matrix and where the leachant is a complex reactor in which chemistry coupled with inter-phase mass transfer and convection processes take place. It is demonstrated here that the modelling of open reactors (convection) is possible with PHREEQC by using RATES and KINETICS keyword data blocks. The PHREEQC model was validated by results comparison with analytical solutions of the system equations. Coupling a diffusion compartment with an open reactor (complex boundary conditions for the diffusion equation) requires the introduction of a stagnant cell on the first grid cell of the diffusion compartment in TRANSPORT data block and the use of MIX function for model the monolith/leachant interface transfer. The proposed model was validated by comparison with numerical solutions obtained with MATLAB and by a numerical sensibility study. Finally, the model equations are given for a complex dynamic leaching process of a porous monolith involving beside reaction/diffusion in the monolith, reactions, interface mass transfers, gas absorption and convection in the leachant. Examples of PHREEQC modelling are presented: (1) the case of continuous leaching of a cement based material using carbonated water and (2) a field scale water storage pool constructed with a solidified/stabilised material. The comparison with the experimental leaching data shows the simulation results are very satisfying. (C) 2008 Elsevier B.V All rights reserved.