Metal dissociation from humic colloids: Kinetics with time-dependent rate constants

The mobility of contaminant metals in aqueous subsurface environments is largely controlled by their interaction with humic substances as colloidal constituents of Dissolved Organic Matter. Transport models for predicting carrier-bound migration are based on a competitive partitioning process between solid surface and colloids. However, it has been observed that dissociation of multivalent metals from humic complexes is a slow kinetic process, which is even more impeded with increasing time of contact. Based on findings obtained in isotope exchange experiments, the convoluted time dependence of dissociation was fully described by a complex two-site approach, integrating rate "constants" that are in turn time-dependent. Thus, this study presents the treatment of a particular phenomenon: kinetics within kinetics. The analysis showed that the inertization process does not lead to irreversible binding. Consequently, thermodynamic concepts using equilibrium constants remain applicable in speciation and transport modeling if long time frames are appropriate.