Biogenic and anthropogenic sources of isoprene and monoterpenes and theirsecondary organic aerosol in Delhi, India

Isoprene and monoterpene emissions to the atmosphere are generally dominated by biogenic sources. The oxidation of these compounds can lead to the production of secondary organic aerosol; however the impact of this chemistry in polluted urban settings has been poorly studied. Isoprene and monoterpenes can form secondary organic aerosol (SOA) heterogeneously via anthropogenic-biogenic interactions, resulting in the formation of organosulfate (OS) and nitrooxy-organosulfate (NOS) species. Delhi, India, is one of the most polluted cities in the world, but little is known about the emissions of biogenic volatile organic compounds (VOCs) or the sources of SOA. As part of the DELHI-FLUX project, gas-phase mixing ratios of isoprene and speciated monoterpenes were measured during pre- and post-monsoon measurement campaigns in central Delhi. Nocturnal mixing ratios of the VOCs were substantially higher during the post-monsoon (isoprene: (0.65 +/- 0.43) ppbv; limonene: (0.59 +/- 0.11) ppbv; alpha-pinene: (0.13 +/- 0.12) ppbv) than the pre-monsoon (isoprene: (0.13 +/- 0.18) ppbv; limonene: 0.011 +/- 0.025 (ppbv); alpha-pinene: 0.033 +/- 0.009) period. At night, isoprene and monoterpene concentrations correlated strongly with CO during the post-monsoon period. Filter samples of particulate matter less than 2.5 mu m in diameter (PM2.5) were collected and the OS and NOS content analysed using ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS2). Inorganic sulfate was shown to facilitate the formation of isoprene OS species across both campaigns. Sulfate contained within OS and NOS species was shown to contribute significantly to the sulfate signal measured via AMS. Strong nocturnal enhancements of NOS species were observed across both campaigns. The total concentration of OS and NOS species contributed an average of (2.0 +/- 0.9) % and (1.8 +/- 1.4) % to the total oxidized organic aerosol and up to a maximum of 4.2 % and 6.6 % across the pre- and post-monsoon periods, respectively. Overall, this study provides the first molecular-level measurements of SOA derived from isoprene and monoterpene in Delhi and demonstrates that both biogenic and anthropogenic sources of these compounds can be important in urban areas.