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The identification of selenopolythionates in aqueous solutions by electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry
Talanta ( IF 6.1 ) Pub Date : 2020-10-15 , DOI: 10.1016/j.talanta.2020.121770
Jacob Bothen , Dirk Wallschläger

Selenosulfate (SeSO32−) has been shown to occur in certain industrial process waters, and selenopolythionates (SenSxO62−) can be suspected to form from SeSO32− via oxidative or addition reactions. We report here the first observation of selenopolythionates in waters by mass spectrometry. The high mass accuracy and ultra-high resolution of Fourier transform-ion cyclotron resonance-mass Spectrometry with electrospray ionization (ESI-FT-ICR-MS) were used to analyze the isotope patterns of selenium (Se), sulfur (S), and oxygen (O) satellites, in order to provide unequivocal determination of the molecular sum formula of three different selenopolythionates. An aged aqueous solution of SeSO32− was shown to contain the sodium adducts of selenotrithionate (NaSeS2O6), diselenotetrathionate (NaSe2S2O6), and triselenopentathionate (NaSe3S2O6). The identity of these ions was confirmed by accurate mass determination (Δ m/z < 3 ppm error) and by isotopic intensity ratio analysis of the [MIS+2] satellites. Furthermore, Collision Induced Dissociation (CID) was applied to selenotrithionate to distinguish between isomers, and the fragmentation mass spectrum reveals that the Se atom in NaSeS2O6 is located in the middle of the chalcogen chain. Ion chromatographic analysis of the analyzed selenosulfate solutions indicates that selenopolythionates are not suitable for determination by common separations employed for Se speciation analysis, which emphasizes the value of ESI-FT-ICR-MS for complete qualitative characterization of trace element speciation in solution.



中文翻译:

电喷雾电离-傅立叶变换-离子回旋共振质谱法鉴定水溶液中的硒代多硫酸盐

硒代硫酸盐(SeSO 3 2-)已显示在某些工业生产用水中,硒多硫酸盐(Se n S x O 6 2-)可能被怀疑是由SeSO 3 2-形成的。通过氧化或加成反应。我们在这里报告通过质谱法对水域中的硒代多硫氰酸酯的首次观察。使用电喷雾电离的傅立叶变换离子回旋共振质谱(ESI-FT-ICR-MS)的高质量准确度和超高分辨率来分析硒(Se),硫(S)和氧(O)卫星,以便提供对三种不同的硒代多硫代酸酯的分子总和式的明确确定。SESO的老化水溶液3 2-显示含有selenotrithionate的钠加合物(的NAS 2 ö 6 - ),diselenotetrathionate(核苷酸酶2小号2 ö 6 -),以及triselenopentathionate(核苷酸酶3小号2 ö 6 - )。这些离子的身份通过精确的质量测定(Δm / z <3 ppm误差)和[MIS + 2]卫星的同位素强度比分析得到确认。此外,碰撞诱导解离(CID)施加到selenotrithionate异构体之间进行区分,并且碎片质谱表明,硒原子中的NAS 2 ö 6 -位于硫族元素链的中间。所分析的硒代硫酸盐溶液的离子色谱分析表明,硒代多硫酸盐不适合用于硒形态分析的常规分离方法测定,这强调了ESI-FT-ICR-MS对于溶液中痕量元素形态的完整定性表征的价值。

更新日期:2020-10-30
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