Environmental Sensing of Aquatic Systems at the University of Geneva.

Aquatic environments are complex living systems where biological and chemical constituents change rapidly with time and space and may exhibit synergistic interactions. To understand these processes, the traditional approach based on a typically monthly collection of samples followed by laboratory analysis is not adequate. It must be replaced by high-resolution autonomous in situ detection approaches.

Limits of the linear accumulation regime of DGT sensors.

A key question for the practical application of DGT (Diffusive Gradients in Thin films) as dynamic sensors in the environmental monitoring of trace metals is the influence of pH and dissolved ligands over the linear accumulation regime. Protons compete with metal ions for the binding to the DGT resin sites at relatively low pH, whereas high affinity dissolved ligands compete with resin sites for the binding of metals. Any of the two phenomena can lead to a departure from the linear accumulation regime and an underestimation of the actual species concentration in solution.

Lability criteria in diffusive gradients in thin films.

The penetration of metal complexes into the resin layer of DGT (diffusive gradients in thin films) devices greatly influences the measured metal accumulation, unless the complexes are either totally inert or perfectly labile. Lability criteria to predict the contribution of complexes in DGT measurements are reported. The key role of the resin thickness is highlighted.

Contribution of partially labile complexes to the DGT metal flux.

Penetration of complexes into the resin layer can dramatically increase the contribution of complexes to the metal flux measured with a DGT (diffusive gradients in thin films) sensor, but equations to describe this phenomenon were not available. Here, simple approximate analytical expressions for the metal flux, the lability degree and the concentration profiles in a DGT experiment are reported. Together with the thickness of the reaction layer in the gel domain, the effective penetration distance into the resin layer that would be necessary for full dissociation of the complex (λ(ML)) plays a key role in determining the metal flux.

Key role of the resin layer thickness in the lability of complexes measured by DGT.

Analysis of the dynamic features of diffusion gradients in thin film devices (DGT) indicates that the penetration of complexes into the resin layer dramatically increases their lability. This should be taken into account when interpreting DGT measurements in terms of the dynamics of solution speciation. The experimental accumulation of Cd by DGT sensors in Cd-NTA systems confirmed these theoretical analyses.

Effective affinity distribution for the binding of metal ions to a generic fulvic acid in natural waters.

The effective distribution of affinities (Conditional Affinity Spectrum, CAS) seen by a metal ion binding to a humic substance under natural water conditions is derived and discussed within the NICA-Donnan model. Analytical expressions for the average affinity of these distributions in general multi-ion mixtures are reported here for the first time. These expressions enable a simple evaluation of the effect of all interfering cations on the affinity distribution of a given one.