Capillary geochemistry in non-saturated zone of soils. Water content and geochemical signatures

The unsaturated zone (UZ) retains aqueous solutions against gravity by capillary forces. This suction state corresponds to a decreasing internal pressure of the water, which modifies its thermodynamic properties. Accordingly, the speciation of solutes and the solubility of solids and gases in such capillary solutions change. The volumetric capillary water content of the soil at high suction can be calculated extrapolating the water retention curves (WRC) with the Rossi–Nimmo model. Interestingly, several tens of liters per cubic meter of soil can be thus suctioned, a sufficiently large volume to support that: (1) capillary water is not restricted to nanosized pores, which means it disobeys the Young–Laplace law and is metastable with respect to vapor (superheating); and (2) the geochemistry of capillary solutions might significantly influence the subsurface mass transfer. Two field situations are here interpreted using the capillary thermodynamic properties: (1) the trapping of sand grains during the growth of desert roses (gypsum), and (2) the development of abnormal paragenetic sequences in some saprolites.