Metal (Pb, Cd, and Zn) Binding to Diverse Organic Matter Samples and Implications for Speciation Modeling

This study evaluated the influence of dissolved organic matter (DOM) properties on the speciation of Pb, Zn, and Cd. A total of six DOM samples were categorized into autochthonous and allochthonous sources based on their absorbance and fluorescence properties. The concentration of free metal ions ( C_M²⁺) measured by titration using the absence of gradients and Nernstian equilibrium stripping (AGNES) method was compared with that predicted by the Windermere humic aqueous model (WHAM). At the same binding condition (pH, dissolved organic carbon, ionic strength, and total metal concentration) the allochthonous DOM showed a higher level of Pb binding than the autochthonous DOM (84- to 504-fold C_Pb²⁺ variation). This dependency, however, was less pronounced for Zn (12- to 74-fold C_Zn²⁺ variation) and least for Cd (2- to 14-fold C_Cd²⁺ variation). The WHAM performance was affected by source variation through the active DOM fraction ( F). The commonly used F = 1.3 provided reliable C_Pb²⁺ for allochthonous DOMs and acceptable C_Cd²⁺ for all DOM, but it significantly under-predicted C_Pb²⁺ and C_Zn²⁺ for autochthonous DOM. Adjusting F improved C_M²⁺ predictions, but the optimum F values were metal-specific (e.g., 0.03-1.9 for Pb), as shown by linear correlations with specific optical indexes. The results indicate a potential to improve WHAM by incorporating rapid measurement of DOM optical properties for site-specific F.