In Situ Measurement of Thallium in Natural Waters by a Technique Based on Diffusive Gradients in Thin Films Containing a δ-MnO2 Gel Layer

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 avoid 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 gradients 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 kinetics of Tl demonstrated that δ-MnO2 binding gels could adsorb Tl rapidly and effectively. Removal of Tl from the δ-MnO2 gels was achieved by use of 1 mol·L–1 oxalic acid, yielding elution efficiencies of 1.0 for Tl(I) and 0.86 for TI(III). Theoretical responses from DGT devices loaded with δ-MnO2 gel (δ-MnO2-DGT) were obtained irrespective of pH (4–9) and ionic ...