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

Hongmei Deng, Mengting Luo, Xinyao Shi, Paul N. Williams, Kexin Li, Meiling Liu, Weiye Fan, Tangfu Xiao, Yongheng Chen, Lena Q. Ma, Jun Luo

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Abstract

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 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 kept in solution, containing only 10 mmol·L–1 NaNO3, for at least 117 days. 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 technique shows potential for environmental monitoring and biogeochemical investigation of Tl in waters.
Original languageEnglish
Pages (from-to)1344–1352
JournalAnalytical Chemistry
Volume91
Issue number2
Early online date18 Dec 2018
DOIs
Publication statusPublished - 15 Jan 2019

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