Preprints
https://doi.org/10.5194/acp-2021-1033
https://doi.org/10.5194/acp-2021-1033

  21 Dec 2021

21 Dec 2021

Review status: this preprint is currently under review for the journal ACP.

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

Varun Kumar1, Stamatios Giannoukos1,a, Sophie L. Haslett2, Yandong Tong1, Atinderpal Singh3,b, Amelie Bertrand1, Chuan Ping Lee1, Dongyu S. Wang1, Deepika Bhattu1,c, Giulia Stefenelli1, Jay S. Dave3, Joseph V. Puthussery4, Lu Qi1, Pawan Vats5, Pragati Rai1, Roberto Casotto1, Rangu Satish3, Suneeti Mishra6, Veronika Pospisilova1,d, Claudia Mohr2, David M. Bell1, Dilip Ganguly5, Vishal Verma4, Neeraj Rastogi3, Urs Baltensperger1, Sachchida N. Tripathi6, André S. H. Prévôt1, and Jay G. Slowik1 Varun Kumar et al.
  • 1Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
  • 2Department of Environmental Science, Stockholm University, Sweden
  • 3Geosciences Division, Physical Research Laboratory, Ahmedabad 380009, India
  • 4University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States
  • 5Centre for Atmospheric Sciences, Indian Institute of Technology Delhi, New Delhi 110016, India
  • 6Department of Civil Engineering and Centre for Environmental Science and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
  • anow at: ETH Zurich, Department of Chemistry and Applied Biosciences, 8093 Zurich, Switzerland
  • bnow at: Department of Environmental Studies, University of Delhi, Delhi 110007, India
  • cnow at: Department of Civil and Infrastructure Engineering, Indian Institute of Technology Jodhpur, 342037, India
  • dnow at: Tofwerk AG, Uttigenstrasse 22, 3600 Thun, Switzerland

Abstract. In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution, especially during winters. Comprehensive knowledge of the composition and sources of the organic aerosol (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary OA (POA) and showed that secondary OA (SOA) played a major role, but were unable to resolve specific SOA sources. We address the latter through the first field deployment of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer (AMS). Measurements were conducted during the winter of 2018/2019, and positive matrix factorization (PMF) was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning OA (BBOA-1 and 2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LO-OOA). On average, 40 % of the total OA mass was apportioned to the secondary factors. The SOA contribution to total OA mass varied greatly between daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %, 21:00–04:00 local time). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin: aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA dominated factors were related to the total AMS SOA (i.e., MO-OOA + LO-OOA) by multi-linear regression (MLR). Aromatic SOA was the major SOA component during the day-time, with 55.2 % contribution to total SOA mass (42.4 % contribution to total OA). Its contribution to total SOA, however, decreased to 25.4 % (7.9 % of total OA) during night-time. This factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA accounted for 18.4 % of total SOA mass (14.2 % of total OA) during day-time and 36.1 % of total SOA mass (11.2 % of total OA) during night-time. Aged biomass burning and mixed urban SOA accounted for 15.2 % and 11.0 % of total SOA mass ( 11.7 % and 8.5 % of total OA mass) during day-time respectively and 15.4 % and 22.9 % of total SOA mass (4.8 % and 7.1 % of total OA mass) during night-time, respectively. A simple dilution/partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed day-time concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production, likely from the oxidation of locally emitted VOCs. In contrast, biogenic SOA was related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study show that in Delhi, the night-time high concentrations are caused by POA emissions led by traffic and biomass burning, and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction. Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the day-time suggests an increased OA toxicity and health-related consequences for the general public.

Varun Kumar et al.

Status: open (until 02 Feb 2022)

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Varun Kumar et al.

Varun Kumar et al.

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Short summary
Here we present source apportionment results from the first field deployment in Delhi of an extractive electrospray ionisation time-of-flight mass spectrometer (EESI-TOF). The EESI-TOF is a recently developed instrument capable of providing uniquely detailed online chemical characterization of OA, in particular the SOA fraction. Here, we are able to apportion not only POA but also SOA to specific sources, which is done for the first time in Delhi.
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