The lability of zinc humate species

Abstract

At low pH, interaction between zinc(II) ions and humic acids yields sparingly soluble surface complexes; in alkaline conditions there are soluble complexes which differ in stability, stoichiometry and lability. The distribution of zinc between ‘fixed’, ‘non-labile’ and ‘labile’ complex forms at different pH values has been evaluated by equilibrating Zn-loaded humic acid (20 to 300 nmol μmol−1) with ion exchange resins of different types (and counter ion forms). Analysis of the supernatant aqueous phase determined the non-labile soluble zinc content (at the equilibrium pH); the ‘labile’ fraction value was found by back-extracting the washed resins into 0.05 M EDTA (pH 7). When the system pH was <6, about 5% was released as a soluble non-labile complex and the majority of the Zn remained firmly fixed to the solid phase. Above pH 6, the substrate dissolved and the percentage present as non-labile species increased from 5 to 70% as the pH changed from 5 to 8.5. Around pH 7, the labile content peaked at around 90%, but this fraction value dropped to −20% at pH 8.5 (due in part to a lower affinity of zinc for the functional groups on the resin involved). The type of synthetic exchanger used controlled both the system pH and the degree of complex dissociation. The distribution pattern was also influenced by the amount of Zn(II) sorbed on the substrate, the initial weight of humic acid present, and the mixing time (dissolution of the solid phase was slow in acid media). While the ratio of fixed to soluble forms could control migration of the metal ion in environmental systems, it is the labile content which is more likely to be ‘available’ to living matter.