Improved atmospheric trace gas measurements with an aircraft-based tandem mass spectrometer: Ion identification by mass-selected fragmentation studies
Improved atmospheric trace gas measurements with an aircraft-based tandem mass spectrometer: Ion identification by mass-selected fragmentation studies
复制标题
使用机载串联质谱仪改进大气痕量气体测量：通过质量选择碎片研究进行离子识别
DOI：
10.1029/1998jd100003
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发表时间：
1998
影响因子：
--
通讯作者：
F. Arnold
中科院分区：
文献类型：
--
作者：
T. Reiner;O. Möhler;F. Arnold
我们建造并使用了机载三重四极杆质谱仪 (TQMS)，用于对对流层上部和平流层下部的质量选择离子的碎片研究。碎片研究包括与离子分子反应质谱 (IMRMS) 测量大气痕量气体相关的环境离子和人工产生的离子，并明确鉴定了用于 IMRMS 测量的重要离子的化学成分。其中包括 CO3−(H2O)n 和 H3O+(H2O)n 离子与 HNO3、SO2、丙酮、HCN 和甲基氰的离子分子反应的产物离子。这些反应已在实验室中进行了研究，并且先前已在大气 IMRMS 光谱中观察到与预期产物离子具有相同质量的离子。目前的碎片研究首次在飞机测量对流层上部和平流层下部期间实际识别这些离子的化学成分，并证明这些离子可以可靠地用于大气痕量气体测量。此外，碎片研究表明了先前未知离子的存在和可能的识别。其中，CO3−H2O2 的初步鉴定为通过 IMRMS 灵敏测量 H2O2 提供了可能性。碎片研究同时还使用 TQMS 对大气痕量气体进行 IMRMS 测量。显示了 HNO3、SO2 的海拔剖面和 H2O2 的下限。
We have built and employed an aircraft-borne triple quadrupole mass spectrometer (TQMS) for fragmentation studies of mass-selected ions in the upper troposphere and lower stratosphere. The fragmentation studies included both ambient and artificially produced ions relevant for the measurement of atmospheric trace gases by ion molecule reaction mass spectrometry (IMRMS) and led to an unambiguous identification of the chemical composition of important ions used for IMRMS measurements. Among these are the product ions of ion molecule reactions of CO3−(H2O)n and H3O+(H2O)n ions with HNO3, SO2, acetone, HCN, and methyl cyanide. These reactions have been studied in the laboratory, and ions having the same masses as the expected product ions have been previously observed in atmospheric IMRMS spectra. The present fragmentation studies are the first to actually identify the chemical composition of these ions during aircraft measurements in the upper troposphere and lower stratosphere and demonstrate that these ions can reliably be used for atmospheric trace gas measurements. Furthermore, the fragmentation studies gave indications for the existence and the possible identification of previously unknown ions. Among these the tentative identification of CO3−H2O2 offers the possibility for sensitive measurements of H2O2 by IMRMS. The fragmentation studies were accompanied by IMRMS measurements of atmospheric trace gases using the TQMS. Altitude profiles of HNO3, SO2, and lower limits for H2O2 are shown.