Use of diffusive gradients in thin-films for studies of chemical speciation and bioavailability

Environmental context The health of aquatic organisms depends on the distribution of the dissolved forms of chemical components (speciation) and their rates of interaction (dynamics). This review documents and explains progress made using the dynamic technique of diffusive gradients in thin-films (DGT) to meet these challenges of measuring directly chemical speciation and associated dynamics in natural waters. The relevance of these measurements to uptake by biota of chemical forms in soils, sediments and water is discussed with reference to this expanding literature. Abstract This review assesses progress in studies of chemical speciation using diffusive gradients in thin-films (DGT) by examining the contributions made by key publications in the last 20 years. The theoretical appreciation of the dynamic solution components measured by DGT has provided an understanding of how DGT measures most metal complexes, but excludes most colloids. These findings strengthen the use of DGT as a monitoring tool and provide a framework for using DGT to obtain in situ kinetic information. Generally, the capabilities of DGT as an in situ perturbation and measurement tool have yet to be fully exploited. Studies that have used DGT to investigate processes relevant to bioavailability have blossomed in the last 10 years, especially for soils, as DGT mimics the diffusion limiting uptake conditions that, under some conditions, characterise uptake by plants. As relationships between element accumulated by DGT and in plants depend on the plant species, soils studied, and the element and its chemical form, DGT is not an infallible predictive tool. Rather its strength comes from providing information on the labile species in the system, whether water, soil or sediment. Recent studies have shown good relationships between measurements of metals in periphyton and by DGT, and unified dose response curves have been obtained for biota in sediments when they are based on DGT measurements. Both these cases suggest that alternative approaches to the established ‘free ion’ approach may be fruitful in these media and illustrate the growing use of DGT to investigate environmental chemical processes.