Freshwaters are recognized as dynamic systems that may be far-removed from equilibrium. A kinetic approach using the competing ligand exchange method with Chelex 100 as the competing ligand and inductively coupled plasmamass spectrometry to measure the dissociation kinetics was used to investigate the chemical speciation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) in model solutions of a well-characterized fulvic acid (Laurentian fulvic acid) and a freshwater sample collected from the Grand River (Ontario, Canada). The kinetic distribution of the metal species were quantitatively characterized by their first-order dissociation rate constants. This kinetic speciation approach has the advantage of providing an objective method for estimating the dissociation rate constants without any a priori assumptions about the number of kinetically distinguishable components or the shape of the distribution. Three factors were found to influence the kinetics of trace metal competition in the freshwater environment: (i) metal-to-ligand ratio, (ii) ionic potential (z2/r), and (iii) ligand field stabilization energy. The results illustrate the importance of considering the valence-shell electron configuration in predicting the kinetics of trace metal competition in the freshwater environment. The markedly slow dissociation kinetics of Ni(II) and Cu(II) species suggest that the usual equilibrium assumption for freshwaters may not be valid. This study has demonstrated the ability of the kinetic model to correctly predict the relative rates of trace metal reactions, indicating that the kinetic model provides a chemically significant description of the kinetic processes in natural waters.

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The kinetic speciation of Co(II), Ni(II), Cu(II), and Zn(II) in model solutions of a well-characterized fulvic acid (Laurentian fulvic acid), freshwater samples from the Rideau River (Ottawa, Ontario), and freshwater samples from the Sudbury (Ontario) area were investigated by the competing ligand exchange method using Chelex 100 as the competing ligand and by inductively coupled plasma-mass spectrometry to measure the dissociation kinetics. The metal species were quantitatively characterized by the rate coefficient for the first-order dissociation of metal complex to free metal ion. This technique can be applied to almost all elements and represents an important advance in our ability to investigate the kinetic availability of metal species in the freshwater environment. The order of the lability of the metal complexes, Co(II) > Ni(II) > Cu(II) < Zn(II), follows the reverse order of the ligand field stabilization energy with the exception of Cu(II); the behavior of Cu(II) is also due to the Jahn-Teller effect, which shortens the equatorial bonds and lengthens the axial bonds of a tetragonally distorted Cu(II)-L6 complex. This study has demonstrated a relationship between the lability of metal-DOM complexes of the 3d transition metals in freshwaters and their d electron configuration. This is the first time that the importance of the d electron configuration on the lability of metal complexes in the freshwater environment has been demonstrated. The slow complexation kinetics of both Ni(II) and Cu(II) suggestthatthe usual equilibrium assumption for freshwaters may be invalid.

Metal complexation properties of dissolved organic carbon (DOC) in freshwaters are recognized but poorly understood. Here, we investigated the release of free nickel from Ni-DOC complexes using nickel-polluted freshwaters from Sudbury (Canada). We used the Competing Ligand Exchange Method with Chelex-100 as the competing ligand to measure the rate of free Ni2+ ion released by the dissociation of Ni-DOC complexes. The kinetic studies showed that the fastest kinetically distinguishable component representing approximately 30-95% of the total nickel had a dissociation rate coefficient similar to that reported for [Ni(H20)6]2+. High concentrations of Ca2+ and Mg2+ caused a larger amount of the DOC-bound nickel to be released as free Ni2+ ion. Growth inhibition of the freshwater alga Pseudokirchneriella subcapitata was highly correlated with the Ni/DOC ratio, the free plus labile nickel concentration, and the dissociation rate coefficient. While the levels of metals were not sufficient to kill Daphnia magna, these test organisms were immobilized in the same samples that showed algal growth inhibition. Only one sample caused 22% death of Hydra attenuata. The algal toxicity tests were consistent with the kinetic speciation results and are consistent with the hypothesis that dissolved [Ni(H20)6]2+ plus other labile nickel species are toxic forms of Ni present.