Simulation of calcite dissolution and porosity changes in saltwater mixing zones in coastal aquifers

Abstract

Thermodynamic models of aqueous solutions have indicated that the mixing of seawater and calcite‐saturated fresh groundwater can produce a water that is undersaturated with respect to calcite. Mixing of such waters in coastal carbonate aquifers could lead to significant amounts of limestone dissolution. The potential for such dissolution in coastal saltwater mixing zones is analyzed by coupling the results from a reaction simulation model (PHREEQE) with a variable density groundwater flow and solute transport model. Idealized cross sections of coastal carbonate aquifers are simulated to estimate the potential for calcite dissolution under a variety of hydrologic and geochemical conditions. Results show that limestone dissolution in mixing zones is strongly dependent on groundwater flux and nearly independent of the dissolution kinetics of calcite. The amount of dissolution varies within a mixing zone, depending on the properties, physical dimensions, and boundary conditions of the aquifer system. Nearly all of the dissolution occurs in the fresher side of the mixing zone, with the maximum dissolution occurring in water that is fresher than that predicted solely by geochemical reaction models. The greatest porosity and permeability development occur at the toe and at the top of the mixing zone. If permeability increases as porosity increases, asymmetry in the dissolution causes the mixing zone to migrate landward over time. Dissolution rates indicated by the model show that this mechanism can produce significant increases in porosity and permeability over time spans on the order of tens of thousands of years. Given the comparatively long span of geologic time, this process may be largely responsible for porosity and permeability development observed in those carbonate rocks through which a freshwater‐saltwater mixing zone had at one time migrated.