Reactive chlorine-, sulfur-, and nitrogen-containing volatile organic compounds impact atmospheric chemistry in the megacity of Delhi during both clean and extremely polluted seasons

Abstract. Volatile organic compounds (VOCs) 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-19). Here, using a new extended volatility range high-mass-resolution (10 000–15 000) proton transfer reaction time-of-flight mass spectrometer, we measured and analysed ambient VOC mass spectra acquired continuously over a 4-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 µg m−3 and were > 4 times in the polluted season relative to the cleaner season, as driven by enhanced emissions from biomass burning and reduced atmospheric ventilation (∼ 2). Among 111, 56 were oxygenated, 10 contained nitrogen, 2 chlorine, 1 sulfur, and 42 were pure hydrocarbons. VOC levels during polluted periods were significantly higher than most developed world megacities. 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 the post-monsoon season, along with 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.