Thallium (Tl) has been identified as a priority contaminant because of its severe toxic effects. Exact measurement of Tl is a challenge because it is difficult to avoided altering the element's chemical speciation during sampling, transport, and storage. In situ measurement may be a good choice. Based on the in situ technique of Diffusive Gradient in Thin-films (DGT), new DGT devices equipped with novel laboratory-synthesized manganese oxide (δ-MnO2) binding gels were developed and systematically validated for the measurement of Tl, including Tl(I) and Tl(III) species, in water. Comparison between Chelex binding gel and δ-MnO2 gel on the uptake kinetic of Tl demonstrated that δ-MnO2 binding gels could adsorb Tl rapidly and effectively. Removal of Tl from the δ-MnO2 gels was achieved using 1 mol L-1 oxalic acid, yielding elution efficiencies of 1.0 and 0.86 respectively for both Tl(I) and TI(III). Theoretical responses from DGT devices loaded with δ-MnO2 gel (δ-MnO2-DGT) were obtained irrespective of pH (4-9) and ionic strength (0.1-200 mmol L-1 NaNO3). δ-MnO2-DGT showed good potential for long-term monitoring of Tl due to its high adsorption capacity of 27.1 μg cm-2 and the stable performance of δ-MnO2 binding gel stored in 0.01 mol L-1 NaNO3 solution for at least 117 d. Field deployment trials confirmed that δ-MnO2-DGT can accurately measure the time-averaged concentrations of Tl in fluvial watercourses. In summary, the newly developed δ-MnO2-DGT shows potential for environmental monitoring and biogeochemical investigation of Tl in waters, sediments, and soils.

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