Gas chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization for fluorotelomer alcohols and perfluorinated sulfonamides determination.

Gas chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization for fluorotelomer alcohols and perfluorinated sulfonamides determination.
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DOI:
10.1016/j.chroma.2015.08.016
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发表时间:
2015-09
期刊:
Journal of chromatography. A
影响因子:
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通讯作者:
T. Portolés;Luis E. Rosales;Juan V. Sancho;F. Javier Santos;E. Moyano
T. Portolés;Luis E. Rosales;Juan V. Sancho;F. Javier Santos;E. Moyano
中科院分区:
其他
文献类型:
--
作者:
T. Portolés;Luis E. Rosales;Juan V. Sancho;F. Javier Santos;E. Moyano

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研究了四种含氟调聚物醇(FTOH)(4:2FTOH、6:2FTOH、8:2FTOH和10:2FTOH)和四种N-烷基氟辛烷磺酰胺/乙醇(N-MeFOSA、N-EtFOSA、N-MeFOSE和N-EtFOSE)的APCI电离和源内裂解行为,并与传统的EI和CI进行了比较。在所有情况下,质子化的分子是APCI光谱的基峰,从而有可能选择其作为MS/MS实验的前体离子。随后,CID裂解显示所有FOSA/FOSE(C4 F7和C3 F5)的共同产物离子。尽管如此,不同的功能给出了特征性的模式碎片。例如,FTOHs主要损失H2O + HF,FOSA主要损失SO2和HF,而FOSE主要损失H2O和SO2。研究了线性、重复性和LOD,获得了1至5 fg的仪器LOD。最后,应用到河水和流入和流出的废水样品已进行了调查,以改善检测能力的这种新的源相比,传统上使用的EI/CI源。当比较溶剂和基质中的标准品时,根据信号增强/抑制评价了APCI中的基质效应。未观察到基质效应,样品中发现的浓度范围为1-100 pg L− 1,远低于先前报告的方法获得的LOD。还发现并初步鉴定了未知的相关全氟烷基物质,如FTOH的甲基砜和甲基亚砜类似物。
Ionization and in source-fragmentation behavior of four fluorotelomer alcohols (FTOH) (4:2 FTOH, 6:2 FTOH, 8:2 FTOH and 10:2 FTOH) and four N-alkyl fluorooctane sulfonamides/-ethanols (N-MeFOSA, N-EtFOSA, N-MeFOSE and N-EtFOSE) by APCI has been studied and compared with the traditionally used EI and CI. Protonated molecule was the base peak of the APCI spectrum in all cases giving the possibility of selecting it as a precursor ion for MS/MS experiments. Following, CID fragmentation showed common product ions for all FOSAs/FOSEs (C4F7and C3F5). Nevertheless, the different functionality gave characteristic pattern fragmentations. For instance, FTOHs mainly loss H2O + HF, FOSAs showed the losses of SO2and HF while FOSEs showed the losses of H2O and SO2. Linearity, repeatability and LODs have been studied obtaining instrumental LODs between 1 and 5 fg. Finally, application to river water and influent and effluent waste water samples has been carried out in order to investigate the improvements in detection capabilities of this new source in comparison with the traditionally used EI/CI sources. Matrix effects in APCI have been evaluated in terms of signal enhancement/suppression when comparing standards in solvent and matrix. No matrix effects were observed and concentrations found in samples were in the range of 1–100 pg L−1far below the LODs achieved with methods previously reported. Unknown related perfluoroalkyl substances, as methyl-sulfone and methyl-sulfoxide analogues for FTOHs, were also discovered and tentatively identified.