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Measurements of trace metal species in situ in a softwater river, a hardwater lake, and a hardwater stream were compared to the equilibrium distribution of species calculated using two models, WHAM 6, incorporating humic ion binding model VI and visual MINTEQ incorporating NICA−Donnan. Diffusive gradients in thin films (DGT) and voltammetry at a gel integrated microelectrode (GIME) were used to estimate dynamic species that are both labile and mobile. The Donnan membrane technique (DMT) and hollow fiber permeation liquid membrane (HFPLM) were used to measure free ion activities. Predictions of dominant metal species using the two models agreed reasonably well, even when colloidal oxide components were considered. Concentrations derived using GIME were generally lower than those from DGT, consistent with calculations of the lability criteria that take into account the smaller time window available for the flux to GIME. Model predictions of free ion activities generally did not agree with measurements, highlighting the need for further work and difficulties in obtaining appropriate input data.

Several techniques for speciation analysis of Cu, Zn, Cd, Pb, and Ni are used in freshwater systems and compared with respect to their performance and to the metal species detected. The analytical techniques comprise the following:  (i) diffusion gradients in thin-film gels (DGT); (ii) gel integrated microelectrodes combined to voltammetric in situ profiling system (GIME−VIP); (iii) stripping chronopotentiometry (SCP); (iv) flow-through and hollow fiber permeation liquid membranes (FTPLM and HFPLM); (v) Donnan membrane technique (DMT); (vi) competitive ligand-exchange/stripping voltammetry (CLE−SV). All methods could be used both under hardwater and under softwater conditions, although in some cases problems with detection limits were encountered at the low total concentrations. The detected Cu, Cd, and Pb concentrations decreased in the order DGT ≥ GIME−VIP ≥ FTPLM ≥ HFPLM ≈ DMT (>CLE−SV for Cd), detected Zn decreased as DGT ≥ GIME−VIP and Ni as DGT > DMT, in agreement with the known dynamic features of these techniques. Techniques involving in situ measurements (GIME−VIP) or in situ exposure (DGT, DMT, and HFPLM) appear to be appropriate in avoiding artifacts which may occur during sampling and sample handling.

The contamination of aquatic ecosystems by natural and anthropogenic metals has lead to a need to better characterize their impact in the environment. To a large extent, the fate and the (eco)toxicity of these elements in aquatic systems are related to their chemical speciation, which may vary continuously in space and time. Detailed measurements of the fraction of specific metal species or groups of homologous metal species and their variation as a function of the bio-physicochemical conditions of the natural media are thus of prime importance. To determine these metal fractions as well as redox chemical species regulating their distribution (dissolved oxygen, sulfides, iron and manganese oxides), new analytical tools capable of performing in situ, real-time monitoring in both water columns and sediments with minimum perturbation of the media are required. This paper reviews the challenges associated with metal speciation studies, and the progress made with state of the art voltammetric techniques to measure the speciation of metals in situ. More specifically, it summarizes the specific conceptual, analytical, and technical criteria that must be considered and/or fulfilled to develop rugged, field deployable, non-perturbing sensors and probes. Strategies used to satisfy these criteria are presented by describing the up-to-date most advanced voltammetric sensors, mini-/micro-integrated analytical systems, and submersible equipments developed for in situ measurements of trace metals and main redox species in aquatic systems. The spatial and temporal resolutions achieved by these news tools represent a significant advantage over traditional laboratory techniques, while simultaneously remaining cost effective. The application of these tools to aquatic systems is illustrated by several examples of unattended and remote in situ monitoring and/or profiling in water columns and sediments.