Highly time-resolved chemical speciation and source apportionment of organic aerosol components in Delhi, India, using extractive electrospray ionization mass spectrometry

In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution,<br> especially during winters. Comprehensive knowledge of the composition and sources of the organic aerosol<br> (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating<br> effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary<br> OA (POA) and showed that secondary OA (SOA) played a major role but were unable to resolve specific SOA<br> sources. We address the latter through the first field deployment of an extractive electrospray ionization timeof-<br> flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer<br> (AMS). Measurements were conducted during the winter of 2018/19, and positive matrix factorization (PMF)<br> was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded<br> three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning<br> OA (BBOA-1 and BBOA-2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LOOOA).<br> On average, 40%of the total OA mass was apportioned to the secondary factors. The SOA contribution to<br> total OA mass varied greatly between the daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %,<br> 21:00–04:00 LT). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA<br> sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary<br> biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin:<br> aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in<br> the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA-dominated factors were related to the<br> total AMS SOA (i.e. MO-OOA C LO-OOA) by multiple linear regression (MLR). Aromatic SOA was the major<br> SOA component during the daytime, with a 55.2% contribution to total SOA mass (42.4% contribution to total<br> OA). Its contribution to total SOA, however, decreased to 25.4% (7.9% of total OA) during the nighttime. This<br> factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA<br> accounted for 18.4% of total SOA mass (14.2% of total OA) during the daytime and 36.1% of total SOA mass<br> (11.2% of total OA) during the nighttime. Aged biomass burning and mixed urban SOA accounted for 15.2%<br> and 11.0% of total SOA mass (11.7% and 8.5% of total OA mass), respectively, during the daytime and 15.4%<br> and 22.9% of total SOA mass (4.8% and 7.1% of total OA mass), respectively, during the nighttime. A simple<br> dilution–partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed daytime<br> concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged<br> biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production,<br> likely from the oxidation of locally emitted volatile organic compounds (VOCs). In contrast, biogenic SOA was<br> related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study<br> show that in Delhi, the nighttime high concentrations are caused by POA emissions led by traffic and biomass<br> burning and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction.<br> Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the<br> daytime suggests an increased OA toxicity and health-related consequences for the general public. This repository has excel file corresponding to each figures presented in main text published version.