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Complexation of metal ions by dissolved organic matter: modeling and application to real systems

Metal ions are known by their physiological and industrial importance as well as by their environmental risk aspects. To elucidate the behavior of these elements in superficial water bodies, it is necessary to understand the various occurring interactions, mainly those related to the chemical speciation. One of the most important processes that metal species undergo in natural aquatic bodies is their interaction with dissolved organic matter (DOM), which can happen through adsorption, ionic exchange and complexation. In this work, laboratory experiments with Cu(II), Pb(II) and Cd(II) ions and commercial humic acid were made under various conditions (ionic strength and buffering) to test the van den Berg and Kramer complexation model. After the simulation, the model was used to determine the Cu(II), Pb(II) and Cd(II) complexation capacity of natural waters from three important rivers in the state of Maranhao, Brazil (Itapecuru, Bacanga and Pericuma rivers). The dissolved organic carbon (DOC) concentration was used to express the DOM concentration. The results confirmed that there is a strong interaction between the DOM and metal ions, and that the van den Berg and Kramer model (with one coordination site) is suitable for estimating the complexation constant (K) and the ligand site concentration (Lt). The simulated water samples used in the laboratory showed the complexation order: Cu(II) > Cd(II) > Pb(II); and the complexation capacity was directly proportional to the humic acid concentration. We believe that the smaller Cu(II) ionic radius yields a stronger affinity with the DOM. In the experiments with natural waters, the river with more DOC (Bacanga river) showed better complexation capacity; however, the order was Pb(II) > Cu(II) > Cd(II) probably because of the presence of appreciable concentrations of Cu(II) in natural waters.

Dissolved organic matter; Metal ions; humic acids; Complexation equilibrium


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