Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, PR China.
Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, PR China.
Talanta. 2015 Sep 1;142:213-20. doi: 10.1016/j.talanta.2015.04.050. Epub 2015 Apr 27.
A new method based on dispersive liquid liquid microextraction (DLLME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the simultaneous speciation of inorganic arsenic (As), selenium (Se) and tellurium (Te) with sodium diethyldithiocarbamate (DDTC) as both chelating reagent and chemical modifier. As(III), Se(IV) and Te(IV) were transformed into DDTC-chelates at pH 7 and extracted into the fine droplets formed by injecting the binary solution of bromobenzene (extraction solvent) and methanol (dispersive solvent) into the sample solution. After phase separation by centrifugation, As(III), Se(IV) and Te(IV) preconcentrated in the organic phase were determined by ETV-ICP-MS. Total inorganic As, Se and Te were obtained by reducing As(V), Se(VI) and Te(VI) to As(III), Se(IV) and Te(IV) with L-cysteine, which were then subjected to the same DLLME-ETV-ICP-MS process. The concentration of As(V), Se(VI), Te(VI) were calculated by subtracting the concentration of As(III), Se(IV) and Te(IV) from the total inorganic As, Se and Te, respectively. The main factors affecting the microextraction efficiency and the vaporization behavior of target species were investigated in detail. Under the optimal conditions, the limits of detection were 2.5, 8.6 and 0.56 ng L(-1) for As(III), Se(IV) and Te(IV), respectively, with the relative standard deviations (n=7) of 8.5-9.7%. The developed method was applied to the speciation of inorganic As, Se and Te in Certified Reference Materials of GSBZ50004-88, GBW(E)080395 and GBW(E)080548 environmental waters, and the determined values are in good agreement with the certified values. The method was also successfully applied to the simultaneous speciation of inorganic As, Se and Te in different environmental water samples with the recoveries in the range of 86.3-107% for the spiked samples.
建立了一种基于分散液液微萃取(DLLME)与电热蒸发电感耦合等离子体质谱联用(ETV-ICP-MS)的新方法,采用二乙二硫代氨基甲酸钠(DDTC)作为螯合剂和化学修饰剂,同时对无机砷(As)、硒(Se)和碲(Te)进行形态分析。在 pH 7 下,As(III)、Se(IV)和 Te(IV)与 DDTC 形成螯合物,然后将其注入到由溴苯(萃取溶剂)和甲醇(分散溶剂)组成的二元溶液中,萃取到样品溶液中形成的细小液滴中。离心后实现液-液分离,将有机相中预浓缩的 As(III)、Se(IV)和 Te(IV)通过 ETV-ICP-MS 进行测定。用 L-半胱氨酸将 As(V)、Se(VI)和 Te(VI)还原为 As(III)、Se(IV)和 Te(IV),得到总无机 As、Se 和 Te,然后采用相同的 DLLME-ETV-ICP-MS 过程进行处理。通过从总无机 As、Se 和 Te 中分别减去 As(III)、Se(IV)和 Te(IV)的浓度,计算出 As(V)、Se(VI)和 Te(VI)的浓度。详细考察了影响微萃取效率和目标物质蒸发行为的主要因素。在最佳实验条件下,As(III)、Se(IV)和 Te(IV)的检出限分别为 2.5、8.6 和 0.56 ng·L-1,相对标准偏差(n=7)为 8.5-9.7%。该方法用于 GSBZ50004-88、GBW(E)080395 和 GBW(E)080548 环境水样中无机 As、Se 和 Te 的形态分析,测定值与认定值吻合良好。该方法还成功地用于不同环境水样中无机 As、Se 和 Te 的同时形态分析,加标样品的回收率在 86.3-107%之间。