Modeling of non-isothermal multi-component reactive transport in field scale porous media flow systems

Abstract

A general 2-D finite element multi-component reactive transport code, TRANQUI, was developed, using a sequential iteration approach (SIA). It is well suited to deal with complex real-world thermo-hydro-geochemical problems for single-phase variably water saturated porous media flow systems. The model considers a wide range of hydrological and thermodynamic as well as chemical processes such as aqueous complexation, acid-base, redox, mineral dissolution/precipitation, gas dissolution/ex-solution, ion exchange and adsorption via surface complexation. Under unsaturated conditions only water flow is considered, although gas pressures are allowed to vary in space in a depth-dependent manner specified by the user. In addition to the fully iterative sequential approach (SIA), a sequential non-iterative approach (SNIA), in which transport and chemistry are de-coupled, was implemented and tested. The accuracy and numerical performance of SIA and SNIA have been compared using several test cases. The accuracy of SNIA depends on space and time discretization as well as on the nature of the chemical reactions. The capability of the code to model a real case study in the field is illustrated by its application to the modeling of the hydrochemical evolution of the Llobregat Delta aquitard in northeastern Spain over the last 3500 years during when fresh-water flow from a lower aquifer displaced the native saline aquitard waters. Manzano and Custodio carried out a reactive transport model of this case study by using the PHREEQM code and considering water flow, aqueous complexation, cation exchange and calcite dissolution. Their results compare favorably well with measured porewater chemical data, except for some of the cations. Our code is not only able to reproduce the results of previous numerical models, but leads to computed concentrations which are closer to measured data mainly because our model takes into consideration redox processes in addition to the processes mentioned above. A number of sensitivity runs were performed with TRANQUI in order to analyze the effect of errors and uncertainties on cation selectivities.