基于超高分辨质谱的溶解性有机质吸收模式谱图研究

Ultra-high-resolution Mass Spectra of Dissolved Organic Matter in the Absorption Mode

  • 摘要: 傅里叶变换离子回旋共振质谱(Fourier transform ion cyclotron resonance mass spectrometry, FT-ICR MS)是在分子水平上表征溶解性有机质(dissolved organic matter,DOM)等有机混合物化学组成最先进的非靶向分析技术,被广泛用于消毒副产物(disinfection byproducts,DBPs)的高通量分析。与传统的幅度模式相比,傅里叶变换的吸收模式能够显著提高离子峰的信噪比和分辨率。然而,吸收模式在DBPs分析中的研究仍属空白。本研究基于FT-ICR MS技术,以氯化处理地表水和地下水为研究对象,阐明吸收模式在DOM和DBPs分析中的优势。结果表明,相比于幅度模式,吸收模式谱图能够显著(P<0.05)提高DOM和DBPs离子峰的分辨率(约1.89~1.97倍)和信噪比(约1.61~1.73倍),显著降低分子式匹配质量误差和同位素峰强度偏差较大的13C同位素峰的峰强偏差。吸收模式识别出的峰较少,而分子式匹配的数量更多(约为幅度模式的1.21~1.39倍),能够显著提高DBPs离子峰的识别数量。但由于环境浓度下DBPs离子峰的强度较低,吸收模式对DBPs峰的峰强偏差降低效果并不明显。吸收模式在基于FT-ICR MS技术的DOM和包括DBPs在内的新污染物非靶向研究方面具有广泛的应用前景。

     

    Abstract: Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is a state-of-the-art technique for the non-targeted analysis of complex organic mixtures such as dissolved organic matter (DOM) at the molecular level, and has been extensively used in the high-throughput analysis of disinfection byproducts (DBPs). Compared to the traditional magnitude mode, the absorption mode of Fourier transform can considerably improve the signal-to-noise ratio and resolving powder of peaks identified in the FT-ICR MS spectra. However, information regarding the advantages of absorption mode in the analysis of DBPs is still limited. In this study, the FT-ICR MS analysis in the chlorination of surface and groundwater was performed to demonstrate the advantages of the absorption mode for DOM and DBPs analysis. The results showed that, compared with the magnitude mode, the absorption mode can significantly (P<0.05) improve the resolution (1.89-1.97 folds) and signal-to-noise ratio value (1.61-1.73 folds) of DOM, including DBPs, and remarkably reduce the mass error for formula assignment and peak intensity deviation of the peaks with large deviations. The absorption mode identifies fewer peaks but has more assigned formulas (1.21-1.39 folds). Moreover, the absorption mode is mainly favorable to the number of identified peaks for DBPs but has limited effects on decreasing the peak intensity deviation of DBPs peaks due to their low intensity at the environmental levels of chlorination reagents. The results highlight the great potential of the absorption mode technology based on FT-ICR MS for the non-targeted analysis of DOM and emerging pollutants, including DBPs.

     

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