The advances in studies of trace metal speciation and bioavailability since Mark Florence’s 1982 review of the topic, published in Talanta, have been comprehensively reviewed. While the relative merits of kinetic and equilibrium approaches are still being determined, advances in the applications of stripping voltammetry, including the application of microelectrodes and an appreciation of detection windows in both CSV and ASV, have been matched by the introduction of new dynamic techniques including diffusive gradients in thin films (DGTs), permeation liquid membranes (PLMs), and improved applications of chelating resins. There have also been improvements in equilibrium techniques such as ion-selective electrodes and Donnan dialysis. The ability of geochemical speciation models to predict metal complexation by natural organic matter has greatly improved, yet the models still require validation against field measurements.

More reliable and relevant bioassays have been developed using sensitive species such as algae and bacteria, and improved protocols are eliminating uncertainties particularly due to problems with high cell densities, and are allowing more useful comparisons with chemically estimated bioavailability. While the free-ion activity model has provided an improved interpretation of the relative toxicities observed with different metal species, its extension to the biotic ligand model is leading to better predictions of acute effects at least on higher organisms. The extension of such approaches to studies of chronic effects at ‘natural’ concentrations using unicellular organisms remains a challenge, as does the evaluation of whether such approaches are simplified limiting cases of a more dynamic natural situation where chemical reactivity and rates of metal transport could be important.