Effect of humic acid on Cd(II), Cu(II) and Pb(II) uptake by freshwater algae: kinetic and cell wall speciation considerations

The present study examines the effect of humic acid on the uptake kinetics of Cd(II), Cu(II), and Pb(II) by the freshwater alga Chlorella kesslerii. The results demonstrated that the relative proportion of Pb in the cell wall layer is greater than that of the internalized Pb, while internalized Cd and Cu were comparable or greater than the adsorbed metal concentration. In the presence of 10 mg L-1 humic acid (HA), Cd and Cu uptake kinetics were consistent with that predicted by measured free metal concentrations. For Pb, the uptake flux and amount of lead bound to internalization and adsorption sites were an order of magnitude higher than those found at the same free lead ion concentrations in the presence of citric acid. Chemodynamic modeling suggested that the enhancement of the Pb uptake flux in the presence of HA originates from an increasing amount of Pb bound to the internalization sites through a ternary complex formation between lead-humic acid complex and internalization sites. Cell wall speciation calculations indicated that the lead-humic acid complex is the predominant species in the cell wall layer, while for Cu(II) and Cd(II) metal bound to the internalization (Cu) and adsorption (Cd) sites significantly dominated over the M-HA complex. The findings of the work show the relevance of the cell wall layer concentration and speciation and its key role in defining the local equilibrium conditions between metal and internalizations sites. The results of the present kinetic study have important consequences for improvement of the mechanistic understanding of the role of dissolved organic matter in metal uptake in phytoplankton and biogeochemical cycling of metals in the surface waters.