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Environmental context It is now nearly 20 years since the introduction of the technique of diffusive gradients in thin films, which can provide information on solute concentrations and dynamics in sediments, soils and water. The interpretation of these measurements in terms of concentrations relies on simple equations and associated assumptions. This review examines how well they have stood the test of time. Abstract Diffusive gradients in thin films (DGT) is now widely used to measure a range of determinands in waters, soils and sediments. In most cases the mass accumulated is interpreted in terms of a labile form of the component being measured using a simple equation that applies to steady-state conditions. During the past decade several publications have revealed phenomena that question some of the assumptions necessary for use of the simple equation. This review systematically examines the available evidence relating to appropriate geometry, possible charge effects, binding of solutes and ligands to the diffusive gel and filter, the rate of reaction with the binding layer, the effects of solution complexation and kinetic limitation, necessary time for deployment and the measurement of nanoparticles. DGT emerges as a robust monitoring tool for labile components in solution. Although there is evidence, for some conditions, of binding of metals and, more moderately, humic substances to the diffusive gel and filter membrane, this is unlikely to affect DGT measurement in natural waters for deployment times exceeding a few days. Detailed speciation and kinetic studies require a more thorough interpretation of the mass accumulated by DGT. A coherent theory has emerged for relatively simple solutions, but systems with complex heterogeneous ligands, as is the case for natural waters, are challenging. The size discrimination of DGT is still poorly known. Systematic measurements with well characterised nanoparticles are required to define the distribution of pore sizes in the gels and to establish the contribution of natural colloids to the DGT measurement.