It is desirable to directly investigate metal cation binding by dissolved humic substance (HS) in environmental samples without isolation and purification of the HS. This is commonly achieved by the fluorometric titration approach, in which the variations of the HS components' fluorescence when titrated with metal cations, such as cupric ions (Cu<sup>2+</sup>), were commonly resolved by a well-established chemometric tool called parallel factor analysis and fit to a classical nonlin ear equation to obtain cation binding parameters. The nonlinear expression was derived based on the two assumptions that a given HS component (e.g., L) binds Cu<sup>2+</sup> with a 1:1 stoichiometry, forming only the complex LCu, and that other ligands competing with L for Cu<sup>2+</sup> are not explicitly considered. Given the deviations (e.g., the presence of multiple HS components competing for Cu<sup>2+</sup> and a likely 2:1 binding stoichiometry in addition to the 1:1 binding) from the assumptions, the fitting-derived binding parameters reported in past studies are questionable; those studies commonly reported high goodness-of-fit (<i>R</i><sup>2</sup>) as a support of the validity of the assumptions. This study deconstructed the current equation and examined it with two organic ligand components in a simulated study to see what conditions could also yield a good fit. It turned out that high a <i>R</i><sup>2</sup> value ranging between 0.9971 and 1.0 was observed despite the deviations from the above-mentioned assumptions. In addition, this study re-evaluated some published experimental data from these past studies and found that the fitting-derived parameters could not be accounted for based on the above-mentioned assumptions. The findings in this study therefore indicate that the current fluorometric titration approach is problematic when investigating HS component interactions with metal ions in situ. The combination of ion-selective electrode and fluorometric titration may be an alternative to the current fluorometric titration approach alone.

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