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The hydrogel/water partitioning of the various species in the cadmium(II)/soil humic acid (HA) system is studied for two types of gel, using in situ microelectrodic voltammetry. Under the conditions of this work, with HA particles of ca. 25 and 125 nm radius, the CdHA complex is shown to be close to nonlabile toward a 12.5 μm radius microelectrode. This implies that its kinetic contribution to Cd(2+) reduction at the medium/microelectrode interface is practically negligible. The polyacrylamide (PAAm) gels equilibrate with the aqueous medium under significant sorption of HA at the gel backbone/gel medium interface, which in turn leads to induced sorption of Cd(II) in the form of immobilized gel-bound CdHA. The rather high total Cd content of the PAAm gel suggests that the binding of Cd(2+) by the hydrophobically gel-bound HA is stronger than that for dispersed HA particles. Still, the intraparticulate speciation of Cd(II) over Cd(2+) and CdHA corresponds to an intrinsic stability constant similar to that for simple monocarboxylate ligands such as acetate. Alginate gels are negatively charged, and their free [Cd(aq)(2+)] is higher than that in the medium by the corresponding Donnan coefficient. On top of that, Cd(2+) is specifically sorbed by the gel backbone/gel medium interface to reach accumulation factors as high as a few tens. HA and CdHA accumulate in the outer 20 μm film of gel at the gel/water interface of both gels, but they do not penetrate into the bulk of the alginate gel. Overall, the gel/water interface dictates drastic changes in the speciation of Cd/HA as compared to the aqueous medium, with distinct features for each individual type of gel. The results have broad significance, for example, for predictions of reactivity and bioavailability of metal species which inherently involve partitioning and diffusion into diverse gel layers such as biointerfacial cell walls, biofilm matrices, and mucous membranes.

The effects of the physicochemical features of aqueous medium on the mode of partitioning of humic acids (HAs) into a model biomimetic gel (alginate) and a synthetic polyacrylamide gel (PAAm) were explored. Experiments were performed under conditions of different pH and ionic strength as well as in the presence or absence of complexing divalent metal ions. The amount of HA penetrating the gel phase was determined by measuring its natural fluorescence by confocal laser scanning microscopy. In both gel types, the accumulation of HA was spatially heterogeneous, with a much higher concentration located within a thin film at the gel surface. The thickness of the surface film (ca. 15 μm) was similar for both types of gel and practically independent of pH, ionic strength, and the presence of complexing divalent metal ions. The extent of HA accumulation was found to be dependent on the composition of the medium and on the type of gel. Significantly more HA was accumulated in PAAm gel as compared to that in alginate gel. In general, more HA was accumulated at lower background salt concentration levels. The distribution of different types of HA species in the gel body was linked to their behavior in the medium and the differences in physicochemical conditions inside the two phases.

Recent progress in understanding the formation/dissociation kinetics of aquatic metal complexes with complexants in different size ranges is evaluated and put in perspective, with suggestions for further studies. The elementary steps in the Eigen mechanism, i.e., diffusion and dehydration of the metal ion, are reviewed and further developed. The (de)protonation of both the ligand and the coordinating metal ion is reconsidered in terms of the consequences for dehydration rates and stabilities of the various outer-sphere complexes. In the nanoparticulate size range, special attention is given to the case of fulvic ligands, for which the impact of electrostatic interactions is especially large. In complexation with colloidal ligands (hard, soft, and combination thereof) the diffusive transport of metal ions is generally a slower step than in the case of complexation with small ligands in a homogeneous solution. The ensuing consequences for the chemodynamics of colloidal complexes are discussed in detail and placed in a generic framework, encompassing the complete range of ligand sizes.

Alginate gel is representative of polysaccharide-based components of cell walls which contain a large number of negatively charged functional groups. The structural charge gives rise to a Donnan potential in the gel, which impacts significantly on the partitioning of ions between the aqueous medium and the gel. We measured the Donnan potential and partitioning of Cd2+ in alginate gel as a function of ionic strength in the range 1-100 mM. The Cd2+ partition coefficient between gel and medium, as measured by in situ microelectrode voltammetry, reaches values between 10 and 100 in the 0.1-1 mM ionic strength range, and agrees well with Donnan partition calculations based on the charge density of the gels. The total Cd(II) concentration in the gel correlates approximately linearly with the free [Cd2+]gel. The results imply that metal ion activities in the biopolymer gel phase may generally differ drastically from those in the bulk medium to an extent that strongly depends on ionic strength. This feature must be taken into account in estimations of exposure conditions for predictions of bioavailability.