Probing Atmospheric Aerosols by Multimodal Mass Spectrometry Techniques: Revealing Aging Characteristics of Its Individual Molecular Components
Probing Atmospheric Aerosols by Multimodal Mass Spectrometry Techniques: Revealing Aging Characteristics of Its Individual Molecular Components
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DOI：
10.1021/acsearthspacechem.3c00228
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发表时间：
2023-12
影响因子：
3.4
通讯作者：
Kyla Siemens;D. Pagonis;Hongyu Guo;Melinda (Mindy) Schueneman;J. Dibb;P. Campuzano‐Jost;J. Jimenez;Alexander Laskin
中科院分区：
文献类型：
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作者：
Kyla Siemens;D. Pagonis;Hongyu Guo;Melinda (Mindy) Schueneman;J. Dibb;P. Campuzano‐Jost;J. Jimenez;Alexander Laskin
利用多峰质谱技术的协同组合，对生物质燃烧有机气溶胶(OA)进行了详细的化学表征。使用部署在NASA DC-8研究飞机上的高分辨率飞行时间气溶胶质谱仪(HR-ToF-AMS)和萃取式电喷雾电离飞行时间质谱仪(EESI-MS)对OA进行了现场分析。此外，还采集了OA的互补滤膜样品，使用与光电二极管阵列和电喷雾电离高分辨率质谱仪(HPLC-PDA-HRMS)接口的高效液相色谱进行离线实验室分析。在2019年8月3日的一次研究飞行中，重点关注华盛顿州威廉姆斯平原火灾，机载HR-TOF-AMS数据显示，有机硫(OS)物种的大量存在是OA的重要组成部分。这些OS物种是根据其独特的碎片化进行鉴定的。进一步的研究使用高效液相-PDA-HRMS和MS裂解，使我们能够确定这些不寻常的OS物种的分子特征。在研究飞行中发现的主要OS化合物是烷基苯磺酸盐。还鉴定了有机硫酸盐、硝基芳香族和氧化芳香族成分。在HRMS结果的指导下，从实时EESI-MS数据集中检索了选定的单个OA物种的时间分辨老化曲线，以评估它们在排放羽流中的老化演化。值得注意的是，烷基苯磺酸盐物种在大气传输的8小时内表现出显著的稳定性。相比之下，普通有机硫酸盐的表观半衰期很短，低至1.2小时，表明它们对老化很敏感。硝基和含氧芳香族物种的老化相对较慢，平均表观半衰期分别为1.8h和2.2h。
Detailed chemical characterization of biomass burning organic aerosol (OA) was performed using a synergistic combination of multimodal mass spectrometry techniques. OA was analyzed in situ using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an extractive electrospray ionization time-of-flight mass spectrometer (EESI-MS) deployed onboard the NASA DC-8 research aircraft. Additionally, complementary filter samples of OA were collected for offline laboratory analysis using high-performance liquid chromatography interfaced with a photodiode array and an electrospray ionization high-resolution mass spectrometer (HPLC-PDA-HRMS). During a research flight on August 3, 2019, which was focused on the Williams Flats Fire, WA, the onboard HR-ToF-AMS data revealed the abundant presence of organic sulfur (OS) species as prominent components of the OA. These OS species were identified based on their unique fragmentation. Further investigation using HPLC-PDA-HRMS and MSnfragmentation allowed us to identify the molecular characteristics of these unusual OS species. The dominant OS compounds detected during the research flight were found to be alkylbenzene sulfonates. Organosulfate, nitroaromatic, and oxygenated aromatic components of OA were also identified. Guided by the HRMS results, time-resolved aging profiles of selected individual OA species were retrieved from the real-time EESI-MS data sets to evaluate their aging evolution in the emission plume. Notably, the alkylbenzene sulfonate species showed remarkable stability over 8 h of atmospheric transport. In contrast, common organosulfates displayed short apparent half-life times that were as low as 1.2 h, indicating their susceptibility to aging. The nitroaromatic and oxygenated aromatic species exhibited relatively slower aging, with average apparent half-life times of 1.8 and 2.2 h, respectively.