Cu and Zn adsorption to a heterogeneous natural sediment: Influence of leached cations and natural organic matter.

Adsorption of heavy metals by natural sediments has important implications to the fate and transport of contaminants in subsurface environments. Although the importance of major multivalent cations and dissolved organic matter (DOM) in heavy metal adsorption had been previously demonstrated, the leaching of major cations and DOM from sediments and its influence on heavy metal adsorption have not been fully examined. In this study, the concentrations of Ca, Mg, Al, Fe, and natural organic matter that leached from a natural sediment in Cu and Zn adsorption experiments were measured and used in surface complexation models to elucidate their effects on Cu and Zn adsorption. Experimental results showed that the leaching of cations and DOM was substantial and pH-dependent. The leached concentrations of Ca and Mg were reasonably simulated based on BaCl2 extractable Ca and Mg at pH < 5, and Al and Fe activities were accurately predicted for specific pH ranges by assuming solubility control by Al(OH)3 and Fe(OH)3. Visual MINTEQ simulations showed that the leached cations markedly decreased Cu adsorption at pH < 6 and Zn adsorption at pH 3-8. Due to varying affinity for DOM between Cu and Zn, DOM was found to decrease Cu adsorption at pH > 6 due to formation of Cu-DOM aqueous complexes, but increase Zn adsorption at pH 4-7 due to formation of aqueous complexes between DOM and major cations, which reduced competition from these cations against Zn for binding sites on the sediment.