Optimized workflow for unknown screening using gas chromatography high‐resolution mass spectrometry expands identification of contaminants in silicone personal passive samplers
Optimized workflow for unknown screening using gas chromatography high‐resolution mass spectrometry expands identification of contaminants in silicone personal passive samplers
复制标题
使用气相色谱高分辨率质谱法优化未知物筛查工作流程，扩大了硅胶个人被动采样器中污染物的识别范围
DOI：
10.1002/rcm.9048
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发表时间：
2021
影响因子：
2
通讯作者：
Aga, Diana S.
中科院分区：
文献类型：
--
作者：
Travis, Steven C.;Kordas, Katarzyna;Aga, Diana S.
在快速发展的生物医学领域，硅胶腕带已成为监测个人暴露于环境污染物的有价值的被动采样器。一旦部署，硅胶腕带收集和保存丰富的化学信息，可以使用高分辨率质谱法（HRMS）进行查询，以提供广泛的覆盖范围的化学mixture.MethodsGas色谱法耦合到Orbitrap™质谱法（GC/Orbitrap™ MS）被用来同时进行可疑筛选（使用内部数据库）和未知筛选（使用供应商数据库）的提取物从腕带佩戴的志愿者。本研究的目的是优化工作流程，使低水平的优先污染物的检测，具有高可靠性。在这方面，开发了GC/Orbitrap™ MS的数据处理工作流程，使用由农药、阻燃剂、有机磷酸酯和多环芳烃组成的123种环境相关标准的混合物作为测试化合物。并将误报数量减少了50%以上。平均26个化合物具有高置信度的鉴定，7个1级化合物和19个2级化合物，观察到磨损的腕带。通过可疑筛选和回顾性可疑筛选进一步分析数据，以确定额外的36 compounds.ConclusionsThis研究提供了三个重要发现：（1）在处理用于未知分析的复杂样品基质中样品净化的重要性的明确证据，（2）用于使用电子电离HRMS数据识别硅胶腕带采样器中的未知污染物的有价值的工作流程，以及（3）GC/Orbitrap™ MS用于未知有机污染物分析的新应用，其可用于化学组学研究。
RationaleSilicone wristbands have emerged as valuable passive samplers for monitoring of personal exposure to environmental contaminants in the rapidly developing field ofexposomics. Once deployed, silicone wristbands collect and hold a wealth of chemical information that can be interrogated using high‐resolution mass spectrometry (HRMS) to provide a broad coverage of chemical mixtures.MethodsGas chromatography coupled to Orbitrap™ mass spectrometry (GC/Orbitrap™ MS) was used to simultaneously perform suspect screening (using in‐house database) and unknown screening (using vendor databases) of extracts from wristbands worn by volunteers. The goal of this study was to optimize a workflow that allows detection of low levels of priority pollutants, with high reliability. In this regard, a data processing workflow for GC/Orbitrap™ MS was developed using a mixture of 123 environmentally relevant standards consisting of pesticides, flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons as test compounds.ResultsThe optimized unknown screening workflow using a search index threshold of 750 resulted in positive identification of 70 analytes in validation samples, and a reduction in the number of false positives by over 50%. An average of 26 compounds with high confidence identification, 7 level 1 compounds and 19 level 2 compounds, were observed in worn wristbands. The data were further analyzed via suspect screening and retrospective suspect screening to identify an additional 36 compounds.ConclusionsThis study provides three important findings: (1) a clear evidence of the importance of sample cleanup in addressing complex sample matrices for unknown analysis, (2) a valuable workflow for the identification of unknown contaminants in silicone wristband samplers using electron ionization HRMS data, and (3) a novel application of GC/Orbitrap™ MS for the unknown analysis of organic contaminants that can be used in exposomics studies.