The Athabasca's oil sands exploitation is controversial due to its potential risks to water quality but little is known about the temporal changes in the most bioavailable fraction of metal, the free/labile species. In this study, diffusive gradient in thin films (DGT) and the Windermere Humic Aqueous Model (WHAM VII) equilibrium model were used to examine the temporal changes in free/labile metal (Cu, Ni, Zn, Pb) species in three tributaries of the north-flowing Athabasca River in the Athabasca oil sands region (AOSR). The influence of dissolved organic matter (DOM) composition (i.e. fulvic: humic ratio) on modeled Cu and Ni speciation showed a negligible effect on the labile concentration. The best agreements (92 ± 8%) between DGT-labile and WHAM calculated labile concentrations were found assuming the formation of iron oxyhydroxides (FeO(OH)). The agreement was only 70 ± 7% in the presence of inorganic colloidal aluminum oxyhydroxides (AlO(OH)) and in the absence of any inorganic colloids. Together these results suggest that a change in DOM composition had limited impacts on modeled free metal ion concentrations. Although the concentration of the main metal ligand (i.e. DOM), varied from 9 to 40 ppm, no significant temporal differences in the abundance of WHAM-modeled labile species were found, suggesting mobility and bioavailability of Cu, Ni, Pb and Zn were comparable over the 2003–2012 period.