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Gel layer based sensors are increasingly employed for dynamic trace metal speciation analysis in aquatic and soil media, in which humic and fulvic acid species are generally known to be relevant. In DGT (diffusive gradient in thin film), polyacrylamide hydrogels are commonly used for the diffusive gel layer. Various effects of the presence of humic species on the amount of metal detected by DGT have been observed, but the role of the different metal/humic species is still unknown. Recently it was shown that in the absence of metal, humic acid accumulates significantly in the polyacrylamide hydrogel. Here we analyze the extent of this accumulation in the presence of cadmium under various conditions of ionic strength and total humic and fulvic acid concentrations. At millimolar ionic strength level, DET data show significant accumulation of cadmium(II) in the gel phase, on top of some Donnan enrichment. The results are essential for the interpretation of DGT/DET data on metals in the presence of humics, especially in freshwaters.

Gel layer based sensors are increasingly employed for dynamic trace metal speciation analysis in aquatic and soil media. In DGT (Diffusive Gradient in Thin film), polyacrylamide hydrogels are commonly used for the diffusive gel layer. While some effects of humic and fulvic acids on the DGT detection of metal species have been observed, the gel permeation properties of the actual humic and fulvic acid compounds themselves have not been analyzed thus far. Here we show with DET (Diffusive Equilibrium in Thin film) that these natural complexing agents do enter the gel layer, and that humic acids even appear to accumulate in the gel, with enrichment factors typically on the order of 10. The results have consequences for the interpretation of DGT-data on metal fluxes from aquatic media containing humics and fulvics.