Competition of Ca(II) and Mg(II) with Ni(II) for Binding by a Well-Characterized Fulvic Acid in Model Solutions

Competition of Ca(II) and Mg(II) with Ni(II) ions for binding sites of a well-characterized fulvic acid (FA) in model solutions at constant pH and ionic strength was investigated. The Competing Ligand Exchange Method with Chelex-100 and dimethyl glyoxime as the competing ligands was employed to measure the rate of free Ni2+ ion release using graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry, respectively. The Windermere Humic Aqueous Model was used to predict the effect of competition of Ca(II) and Mg(II) on the binding of Ni(II) by the FA. The results show that the presence of high concentrations of Ca(II) and Mg(II) in model solutions has considerable effects on the binding of Ni(II) by the FA. Since the concentrations of Ca(II) and Mg(II) used are 4 orders of magnitude higher than those of Ni(II), Ca(II) and Mg(II) can outcompete Ni(II) for sites where electrostatic interactions dominate, resulting in Ni(II) forming weak Ni(II)−FA complexes that are labile. The significance is that in freshwaters containing humic substances and trace quantities of nickel and major cations, Ca2+ and Mg2+, the competition of Ca2+ and Mg2+ with Ni2+ for binding sites of humic substances produces weak Ni(II)−humate complexes that are labile, releasing free Ni2+ ions.