A hydrogeochemical transport model for an oxidation experiment with pyrite/calcite/exchangers/organic matter containing sand

We report the hydrogeochemical modeling of a complicated suite of reactions that take place during the oxidation of pyrite in a marine sediment. The sediment was equilibrated in a column with MgCl2 solution and subsequently oxidized with H2O2. The oxidation of pyrite triggers dissolution of calcite, cation and proton exchange, and CO2 sorption. The composition of the column effluent was modeled with PHREEQC, a hydrogeochemical transport model. The model was extended with a formal ID transport module which includes dispersion and diffusion. The algorithm solves the advection-reaction-dispersion equation with explicit finite differences in a split-operator scheme. Also, kinetic reactions for pyrite oxidation, calcite dissolution and precipitation, and organic C oxidation were included. Kinetic relations for pyrite oxidation and calcite dissolution were taken from the literature, and a coefficient equivalent to the ratio A/V (surface over volume), was adjusted to fit the experimental data. The comparison of model and experiment shows that ion exchange and sorption are dominant chemical processes in regulating and buffering water quality changes upon the oxidation of pyrite. Cation exchange was assigned to the colloidal fraction ( < 2 μm) and deprotonated organic matter, proton buffering to organic matter, and CO2 sorption to amorphous Fe-oxyhydroxide. These processes have been neglected in earlier modeling studies of pyrite oxidation in natural sediments.