For many years it has been recognised that speciation is a key factor in determining the bioavailability of metal pollutants in the environment. One of the key factors that regulates the speciation, mobility and lability of trace metal pollutants in natural waters is the concentration and nature of organic matter. Metals may bind to dissolved organic matter (DOM) in complexes of varying stability, or adsorb to particulate organic matter and through sedimentation relocate to the sediment. With the biouptake, metals may be released from their complexes. However, understanding of the interaction, the dynamic processes and the kinetic signature of metals and organics, including dissolved organic carbon and biotic ligands remains incomplete. DGT (Diffusive Gradients in Thin films) is a technique that was developed as a robust in situ speciation technique to measure free metal and inorganic and/or organic complexes which can readily dissociate. These so called labile species include a proportion of metals bound to humic substances. The use of a strong binding resin (Chelex) allows pre-concentration of trace metals, confering sufficient sensitivity to enable measurement of metals by DGT in pristine natural systems. Fluxes measured using dynamic techniques, such DGT and voltammetry (more conventional technique), can be affected by the distribution of species, their transport dynamics (diffusion) and the dissociation rates of the complexes. Unravelling this information is challenging and impossible for voltammetry. Manipulation of the physical properties of DGT has enabled the simultaneous derivation of kinetic and speciation information for natural waters. Deployment of multiple DGT devices with a range of diffusion layer thicknesses can provide directly a visually informative kinetic signature for a range of metals, and with more sophisticated interpretation, information on the dissociation rates of complexes. Previous work has shown that it may be possible to understand the kinetics of metal release from its DOC complexes using in situ DGT deployments, potentially allowing assessment of the types of organic matter present in a system. This work focuses on the investigation of the kinetics of the interaction between metals and dissolved organic matters produced by algae in freshwaters. For most metals the rate at which they were released from the organic matter was fast, but release of Al and Cu were kinetically limited. The relationship between Fe and DOC was a defining feature of the kinetic signatures. The in situ kinetic parameters of metal release from the organic complexes obtained by this novel approach are essential for the future development of dynamic models and for advancing our understanding of trace metal bioavailability and biogeochemical processes in aquatic systems.