Preprints
https://doi.org/10.5194/egusphere-2024-1671
https://doi.org/10.5194/egusphere-2024-1671
18 Jun 2024
 | 18 Jun 2024
Status: this preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).

Automated compound speciation, cluster analysis, and quantification of organic vapours and aerosols using comprehensive two-dimensional gas chromatography and mass spectrometry

Xiao He, Xuan Zheng, Shuwen Guo, Lewei Zeng, Ting Chen, Bohan Yang, Shupei Xiao, Qiongqiong Wang, Zhiyuan Li, Yan You, Shaojun Zhang, and Ye Wu

Abstract. The advancement of analytical techniques, such as comprehensive two-dimensional gas chromatography coupled with mass spectrometry (GC×GC-MS), enables the efficient separation of complex organic matrix. Developing innovative methods for data processing and analysis is crucial to unlock the full potential of GC×GC-MS in understanding intricate chemical mixtures. In this study, we proposed an innovative method for the semi-automated identification and quantification of complex organic mixtures using GC×GC-MS. The method was formulated based on self-constructed mass spectrum patterns and the traversal algorithms and was applied to organic vapor and aerosol samples collected from tailpipe emissions of heavy-duty diesel vehicles and the ambient atmosphere. Thousands of compounds were filtered, speciated, and clustered into 26 categories, including aliphatic and cyclic hydrocarbons, aromatic hydrocarbons, aliphatic oxygenated species, phenols and alkyl-phenols, and heteroatom containing species. The identified species accounted for over 80 % of all the eluted chromatographic peaks at the molecular level. A comprehensive analysis of quantification uncertainty was undertaken. Using representative compounds, quantification uncertainties were found to be less than 37.67 %, 22.54 %, and 12.74 % for alkanes, polycyclic aromatic hydrocarbons (PAHs), and alkyl-substituted benzenes, respectively, across the GC×GC space, excluding the first and the last time intervals. From source apportionment perspective, adamantane was clearly isolated as a potential tracer for heavy-duty diesel vehicles (HDDVs) emission. The systematic distribution of N-containing compounds in oxidized and reduced valences was discussed and many of them served as critical tracers for secondary nitrate formation processes. The results highlighted the benefits of developing self-constructed model for the enhanced peak identification, automated cluster analysis, robust uncertainty estimation, and source apportionment and achieving the full potential of GC×GC-MS in atmospheric chemistry.

Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this preprint. The responsibility to include appropriate place names lies with the authors.
Xiao He, Xuan Zheng, Shuwen Guo, Lewei Zeng, Ting Chen, Bohan Yang, Shupei Xiao, Qiongqiong Wang, Zhiyuan Li, Yan You, Shaojun Zhang, and Ye Wu

Status: open (until 14 Aug 2024)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2024-1671', Yutong Liang, 07 Jul 2024 reply
  • RC2: 'Comment on egusphere-2024-1671', Anonymous Referee #2, 20 Jul 2024 reply
Xiao He, Xuan Zheng, Shuwen Guo, Lewei Zeng, Ting Chen, Bohan Yang, Shupei Xiao, Qiongqiong Wang, Zhiyuan Li, Yan You, Shaojun Zhang, and Ye Wu
Xiao He, Xuan Zheng, Shuwen Guo, Lewei Zeng, Ting Chen, Bohan Yang, Shupei Xiao, Qiongqiong Wang, Zhiyuan Li, Yan You, Shaojun Zhang, and Ye Wu

Viewed

Total article views: 350 (including HTML, PDF, and XML)
HTML PDF XML Total Supplement BibTeX EndNote
262 65 23 350 30 11 11
  • HTML: 262
  • PDF: 65
  • XML: 23
  • Total: 350
  • Supplement: 30
  • BibTeX: 11
  • EndNote: 11
Views and downloads (calculated since 18 Jun 2024)
Cumulative views and downloads (calculated since 18 Jun 2024)

Viewed (geographical distribution)

Total article views: 326 (including HTML, PDF, and XML) Thereof 326 with geography defined and 0 with unknown origin.
Country # Views %
  • 1
1
 
 
 
 
Latest update: 24 Jul 2024
Download
Short summary
This study introduces an innovative method for identifying and quantifying complex organic vapors and aerosols. By combining advanced analytical techniques and new algorithms, we categorized thousands of compounds from heavy-duty diesel vehicles and ambient air and highlighted specific tracers for emission sources. The innovative approach enhances peak identification, reduces quantification uncertainties, and offers new insights for air quality management and atmospheric chemistry.