Preprints
https://doi.org/10.5194/egusphere-2024-500
https://doi.org/10.5194/egusphere-2024-500
29 Feb 2024
 | 29 Feb 2024

Discovery of reactive chlorine, sulphur and nitrogen containing ambient volatile organic compounds in the megacity of Delhi during both clean and extremely polluted seasons

Sachin Mishra, Vinayak Sinha, Haseeb Hakkim, Arpit Awasthi, Sachin D. Ghude, Vijay Kumar Soni, Narendra Nigam, Baerbel Sinha, and Madhavan N. Rajeevan

Abstract. Volatile organic compounds significantly impact the atmospheric chemistry of polluted megacities. Delhi is a dynamically changing megacity and yet our knowledge of its ambient VOC composition and chemistry is limited to few studies conducted mainly in winter before 2020 (all pre-covid). Here, using a new extended volatility range high mass resolution (10000–15000) Proton Transfer Reaction Time of Flight Mass Spectrometer10K, we measured and analyzed ambient VOC-mass spectra acquired continuously over a four-month period covering “clean” monsoon (July–September) and “polluted” post-monsoon seasons, for the year 2022. Out of 1126 peaks, 111 VOC species were identified unambiguously. Averaged total mass concentrations reached ~260 µgm-3 and were >4 times in polluted season relative to cleaner season, driven by enhanced emissions from biomass burning and reduced atmospheric ventilation (~2). Among 111, 56 were oxygenated, 10 contained nitrogen, 2 chlorine, 1 sulphur and 42 were pure hydrocarbons. VOC levels during polluted periods were significantly higher than most developed world megacities. Surprisingly, methanethiol, dichlorobenzenes, C6-amides and C9-organic acids/esters, which have previously never been reported in India, were detected in both the clean and polluted periods. The sources were industrial for methanethiol and dichlorobenzenes, purely photochemical for the C6-amides and multiphase oxidation and partitioning for C9-organic acids. Aromatic VOC/CO emission ratio analyses indicated additional biomass combustion/industrial sources in post-monsoon season, alongwith year-round traffic sources in both seasons. Overall, the unprecedented new information concerning ambient VOC speciation, abundance, variability and emission characteristics during contrasting seasons significantly advances current atmospheric composition understanding of highly polluted urban atmospheric environments like Delhi.

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.
Sachin Mishra, Vinayak Sinha, Haseeb Hakkim, Arpit Awasthi, Sachin D. Ghude, Vijay Kumar Soni, Narendra Nigam, Baerbel Sinha, and Madhavan N. Rajeevan

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2024-500', Anonymous Referee #1, 20 Apr 2024
    • AC1: 'Reply on RC1', Vinayak Sinha, 19 Jul 2024
  • RC2: 'Comment on egusphere-2024-500', Anonymous Referee #2, 20 May 2024
    • AC2: 'Reply on RC2', Vinayak Sinha, 19 Jul 2024

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2024-500', Anonymous Referee #1, 20 Apr 2024
    • AC1: 'Reply on RC1', Vinayak Sinha, 19 Jul 2024
  • RC2: 'Comment on egusphere-2024-500', Anonymous Referee #2, 20 May 2024
    • AC2: 'Reply on RC2', Vinayak Sinha, 19 Jul 2024
Sachin Mishra, Vinayak Sinha, Haseeb Hakkim, Arpit Awasthi, Sachin D. Ghude, Vijay Kumar Soni, Narendra Nigam, Baerbel Sinha, and Madhavan N. Rajeevan
Sachin Mishra, Vinayak Sinha, Haseeb Hakkim, Arpit Awasthi, Sachin D. Ghude, Vijay Kumar Soni, Narendra Nigam, Baerbel Sinha, and Madhavan N. Rajeevan

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Short summary
We quantified 111 gases using extended volatility mass spectrometry to understand how changes in seasonality and emissions lead from clean air in monsoon to extremely polluted air in the post-monsoon season in Delhi. Averaged total mass concentrations (260 µgm-3) were >4 times in polluted periods, driven by biomass burning emissions and reduced atmospheric ventilation. Reactive gaseous nitrogen, chlorine and sulphur compounds hitherto un-reported from such a polluted environment were discovered.