Complexation of Cd, Ni, and Zn by DOC in Polluted Groundwater: A Comparison of Approaches Using Resin Exchange, Aquifer Material Sorption, and Computer Speciation Models (WHAM and MINTEQA2)

Abstract

Complexation of cadmium (Cd), nickel (Ni), and zinc (Zn) by dissolved organic carbon (DOC) in leachate-polluted groundwater was measured using a resin equilibrium method and an aquifer material sorption technique. The first method is commonly used in complexation studies, while the second method better represents aquifer conditions. The two approaches gave similar results. Metal−DOC complexation was measured over a range of DOC concentrations using the resin equilibrium method, and the results were compared to simulations made by two speciation models containing default databases on metal−DOC complexes (WHAM and MINTEQA2). The WHAM model gave reasonable estimates of Cd and Ni complexation by DOC for both leachate-polluted groundwater samples. The estimated effect of complexation differed less than 50% from the experimental values corresponding to a deviation on the activity of the free metal ion of a factor of 2.5. The effect of DOC complexation for Zn was largely overestimated by the WHAM model, and it was found that using a binding constant of 1.7 instead of the default value of 1.3 would improve the fit between the simulations and experimental data. The MINTEQA2 model gave reasonable predictions of the complexation of Cd and Zn by DOC, whereas deviations in the estimated activity of the free Ni2+ ion as compared to experimental results are up to a factor of 5.