The ghost component of the mass balances at the Critical Zone scale: the chemical reactivity of immobile water

Abstract:

The critical zone (CZ) is characterized by the duality between mass transport processes such as diffusion and flow of gases, fluids, and solids and localized bio-geochemical interactions especially linked to the “immobile” capillary/adsorbed water. Open questions are towards the role of capillarity onto reactive mechanisms: is there a geochemical signature of capillary water that can change the bio-geochemical balance? The research efforts focused on this issue to develop modeling tools integrating capillary effects at the soil-profile or CZ scale.

Water suction gains geochemical significance when ranging from 20 to 200 MPa, meaning high tension and low amount of stretched water with its specific thermophysical properties (Mercury and Tardy, 2001; Mercury et al., 2003; 2004; Pettenati et al., 2008). Therefore, our interest is directed to the dry end of the water retention curve (WRC). The recent model from Silva and Grifoll (2007) proposed a full-range soil-water retention functions, extending the description to the adsorbed films down to the monolayer thickness. At this stage, it becomes possible to evaluate the role of both capillary pockets and adsorbed films at all water content in the geochemical dynamics of non-saturated soils. We developed from that point by fitting the WRC not through a continuous porous network, but through a decomposition into two porous domains (immobile/mobile domains), each with its own potential-water content law. This amounts to treat the WRC according to an intrinsic dual porosity scheme, and make easier to involve chemical effects at each potential-water content couple.

A simple test simulation is developed with calcite rock kinetically interacting with immobile and mobile water, themselves connected by diffusive and advective gradients in the limits of the immobile-mobile contact area. The reactive transport simulations are run with HP1 (Jacques and Šimůnek, 2005). The mass balance exporting toward groundwater is calculated with and without capillary effects, according to a wide range of conditions (climate, recharge rate, water potential in each domain, etc). It demonstrates how the capillary component acts on the chemical dynamics at the CZ scale.

 Keywords: critical zone, unsaturated zone, capillarity, reactive transport modeling,“stretched water”.