Proton binding by groundwater fulvic acids of different age, origins, and structure modeled with the Model V and NICA−Donnan Model

The proton binding properties of four fulvic acids from pristine groundwater and leachate-polluted groundwater were measured at four different ionic strengths (0.005−0.12 M) and modeled by the Model V and the NICA−Donnan model in order to evaluate the necessity of detailed proton binding parameters for groundwater fulvic acids. The proton binding parameters derived from the various fulvic acids were very similar, and on the basis of these parameters, it was not possible to distinguish between pristine and polluted groundwater. Normalization of the proton charge density by the proton charge density at pH 7 for each fulvic acid made all four fulvic acids regress to the same curve. The effects of varying the proton binding parameters were evaluated by simulating cadmium complexation using sets of proton binding parameters for the four fulvic acids and default sets of proton binding parameters available in the models WHAM (based on Model V) and Ecosat (based on NICA−Donnan). The Model V was rather indifferent with respect to specific characteristics of fulvic acids proton binding, and for most practical uses, the default values available in the model can be used. The NICA−Donnan model resulted in larger deviations between simulations based on default values and specific parameters. However, the NICA−Donnan database is still rather limited, and specific proton binding parameters should be used until the database providing default values has been extended.