Root-zone modeling of heavy metal uptake and leaching in the presence of organic ligands

We present a mechanistic model which describes root uptake and leaching of heavy metals in the plant root zone, accounting for solution- and surface-complexation, (kinetic) mineral dissolution, heavy metal diffusion towards the root, root uptake, root exudation, ligand degradation and convective-dispersive transport of the soluble species. The model was used to simulate the influence of EDTA addition on Cu transport and plant uptake and the effect of oxalate exudation by roots on Cu transport and bioavailability using parameter values from the literature. In the simulations we assumed that free Cu²⁺ is the bioavailable form. Under slightly acidic conditions (pH 6) the model predicted that EDTA stabilizes Cu while at a slightly alkaline pH (pH 7.5), EDTA mobilizes Cu. The addition of EDTA approximately halved the cumulative Cu uptake after 360 days at pH 4.5, and reduced the uptake by a factor of 100 and 1000 at pH 6 and 7.5, respectively. Although the total dissolved concentration was increased, plant uptake was reduced by the formation of bio-inavailable complexes. The exudation of oxalate resulted in a decrease of the Cu concentration breaking through below the root zone, due to sorption of Cu-oxalate. In the presence of dissolved organic carbon (DOC), the exudation of oxalate increased Cu leaching considerably at pH 6 and 7.5. In the absence of DOC, the exudation of oxalate reduced Cu uptake due to the formation and adsorption of Cu-oxalate on goethite surface sites. Exudation of oxalate in the presence of DOC resulted in a further decrease of Cu uptake. Oxalate gradually takes over from DOC in binding Cu due to simultaneous production of oxalate and leaching of DOC. The simulations show that addition or exudation of ligands does not necessarily increase the solubility, transport and bioavailability of metals. Depending on the conditions (mainly the pH), also reduced transport and uptake can be observed, either by formation of ternary surface complexes or reduction of free metal concentration. The model can be easily extended to include further processes.