Adsorptive cathodic stripping voltammetry (AdCSV) in conjunction with the competing ligand-exchange method (CLEM) was investigated as a tool for measuring dissociation rate coefficients of nickel complexes in model systems. Dimethylglyoxime (DMG) was used as the competing ligand. Citric acid (CA) and a well-characterized fulvic acid (FA) were used as model ligands. The rate coefficients were calculated, and the consistency of equilibrium and kinetic data was discussed. The contributions of the disjunctive pathway (proceeding by the dissociation of the initial complex) and the adjunctive pathway (proceeding by the formation of an intermediate complex as a result of direct attack of the competing ligand on the initial complex) on the overall reactions were investigated. The reactions of Ni-CA or Ni-FA complexes with DMG were demonstrated to proceed by both disjunctive and adjunctive pathways. The predominant pathway for the overall reaction depends on the nickel-to-initial ligand and the DMG-to-initial ligand ratios. The reactions follow predominantly the disjunctive pathway for [DMG] > or = 3 mM and Ni-to-dissolved organic carbon (DOC) ratios greater than 10 nM Ni 2+/g of DOC. Since free nickel ion in freshwaters is reported to be toxic, its rate and pathway of formation are of environmental concern.