Department of Applied chemistry, Anhui University of Technology, Maanshan, Anhui 243002, PR China.
Department of Applied chemistry, Anhui University of Technology, Maanshan, Anhui 243002, PR China.
Talanta. 2016 Oct 1;159:127-136. doi: 10.1016/j.talanta.2016.06.009. Epub 2016 Jun 7.
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 0.4A. 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 0.6A, 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 (3s) of As(III), iAs and tAs in aqueous solutions are 0.25μgL(-1), 0.22μgL(-1) and 0.10μgL(-1), respectively. The accuracy of the method is verified through the analysis of standard reference materials (SRM 1568a).
本工作描述了一种新颖的非色谱方法,通过基于修饰石墨电极的电解氢化物发生(EHG),结合原子荧光光谱法(AFS)检测,对砷物种进行准确和选择性的测定。两种含巯基的修饰剂,半胱氨酸(Cys)和谷胱甘肽(GSH),被用于修饰阴极。EHG 性能的砷在修饰阴极上发生了巨大变化,这是以前从未报道过的。在施加电流为 0.4A 时,在 GSH 修饰石墨电极(GSH/GE)上的亚砷酸盐[As(III)]可以被选择性和定量地转化为 AsH3。在施加电流为 0.6A 时,在 Cys 修饰石墨电极(Cys/GE)EHG 上的砷酸盐[As(V)]和砷酸盐[As(V)]可以被选择性和有效地转化为砷烷,而单甲基砷酸(MMA)和二甲基砷酸(DMA)在这种条件下不会形成任何或只有较少的挥发性氢化物。通过改变分析条件,我们还实现了总砷(tAs)和 DMA 的分析。在最佳条件下,水溶液中 As(III)、iAs 和总 As 的检测限(3s)分别为 0.25μgL(-1)、0.22μgL(-1)和 0.10μgL(-1)。通过对标准参考物质(SRM 1568a)的分析验证了该方法的准确性。