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The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.

A multisurface model is used to evaluate the contribution of various sorption surfaces to the control of heavy metal activity in sandy soil samples at pH 3.7-6.1 with different sorbent contents. This multisurface model considers soil as a set of independent sorption surfaces, i.e. organic matter (NICA-Donnan), clay silicate (Donnan), and iron hydroxides (DDL, CD-MUSIC). The activities of Cu2+, Cd2+, Zn2+, Ni2+, and Pb2+ in equilibrium with the soil have been measured using a Donnan membrane technique. The metal activities predicted by the model agree with those measured reasonably well over a wide concentration range for all the metals of interest except for Pb. The modeling results suggest that soil organic matter is the most important sorbent that controls the activity of Cu2+, Cd2+, Zn2+, and Ni2+ in these sandy soils. When metal loading is high in comparison with soil organic matter content, the contribution of clay silicates to metal binding becomes more important. Adsorption to iron hydroxides is found not significant in these samples for Cu, Cd, Zn, and Ni. However, for Pb the model estimates strong adsorption on iron hydroxides. The model predicts that acidification will not only lead to increased solution concentrations but also to a shift toward more nonspecific cation-exchange type binding especially for the metals Cd, Zn, and Ni. Lowering the pH has led to a loss of 56% of Cd, 69% of Zn, and 66% of Ni during 16 years due to increased leaching.

The effects of solid, dissolved organic matter and of pH on copper mobility in a copper-contaminated sandy soil has been studied in the laboratory as well as in the field. The soil, with pH ranging from 3.8 to 5.7, had been polluted with copper in the range from 0.13 to 1.9 mmol/kg more than 1 decade ago. Copper bound by dissolved organic matter (purified humic acid) was determined by a Cu ion selective electrode (Cu-ISE) in a pH range from 4 to 8 and a free copper range from 10-4 to 10-12 mol/L. Column experiments were carried out to investigate the mobility of DOC itself and the effect of DOC on Cu mobility. Copper binding by dissolved organic matter (DOC) as well as copper binding by (soil) solid organic matter (SOC) could be described well with the non-ideal competitive adsorption (NICA) model and with the Two Species Freundlich (TSF) model. Both models could be used to predict the copper concentration at different depths in a field using the total Cu content, pH, and solid and dissolved organic matter content. At pH 3.9 about 30% of the Cu in solution was copper bound by DOC, and at pH 6.6 CuDOC comprised more than 99%. DOC mobility was very sensitive to pH and calcium concentration.