Selective determination of four arsenic species in rice and water samples by modified graphite electrode-based electrolytic hydride generation coupled with atomic fluorescence spectrometry

•A non-chromatographic approach for determining four As species were developed.•Modified graphite electrode-based EHG were used as sample introduction method.•Signals on modified cathode can be improve greatly.•The method is successfully applied in rice and water samples.

This work describes a novel non-chromatographic approach for the accurate and selective determining As species by modified graphite electrode-based electrolytic hydride generation (EHG) for sample introduction coupled with atomic fluorescence spectrometry (AFS) detection. Two kinds of sulfydryl-containing modifiers, l-cysteine (Cys) and glutathione (GSH), are used to modify cathode. The EHG performance of As has been changed greatly at the modified cathode, which has never been reported. Arsenite [As(III)] on the GSH modified graphite electrode (GSH/GE)-based EHG can be selectively and quantitatively converted to AsH3 at applied current of 0.4 A. As(III) and arsenate [As(V)] on the Cys modified graphite electrode (Cys/GE) EHG can be selectively and efficiently converted to arsine at applied current of 0.6 A, whereas monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) do not form any or only less volatile hydrides under this condition. By changing the analytical conditions, we also have achieved the analysis of total As (tAs) and DMA. Under the optimal condition, the detection limits (3 s) of As(III), iAs and tAs in aqueous solutions are 0.25 μg L−1, 0.22 μg L−1 and 0.10 μg L−1, respectively. The accuracy of the method is verified through the analysis of standard reference materials (SRM 1568a).

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