CaltechAUTHORS
Published December 23, 2022 | Version Published
Journal Article Open

An investigation of petrochemical emissions during KORUS-AQ: Ozone production, reactive nitrogen evolution, and aerosol production

Creators

  • 1. ROR icon Georgia Institute of Technology
  • 2. ROR icon California Air Resources Board
  • 3. ROR icon Langley Research Center
  • 4. ROR icon University of Colorado Boulder
  • 5. ROR icon University of California, Irvine
  • 6. ROR icon University of Virginia
  • 7. ROR icon California Institute of Technology
  • 8. ROR icon University of California, Berkeley
  • 9. ROR icon Pennsylvania State University
  • 10. ROR icon University of Oslo
  • 11. ROR icon Universität Innsbruck
  • 12. ROR icon Aerodyne Research
  • 13. ROR icon National Center for Atmospheric Research

Abstract

Emissions and secondary photochemical products from the Daesan petrochemical complex (DPCC), on the west coast of South Korea, were measured from the NASA DC-8 research aircraft during the Korea-United States Air Quality campaign in 2016. The chemical evolution of petrochemical emissions was examined utilizing near-source and downwind plume transects. Small alkenes, such as ethene (C2H4), propene (C3H6), and 1,3-butadiene (C4H6), dominated the hydroxyl (OH) radical reactivity near the source region. The oxidation of these alkenes in the petrochemical plumes led to efficient conversion of nitrogen oxides (NOx) to nitric acid (HNO3), peroxycarboxylic nitric anhydrides (PANs), and alkyl nitrates (ANs), where the sum of the speciated reactive nitrogen contributes more than 80% of NOy within a few hours. Large enhancements of short-lived NOx oxidation products, such as hydroxy nitrates (HNs) and peroxyacrylic nitric anhydride, were observed, in conjunction with high ozone levels of up to 250 ppb, which are attributed to oxidation of alkenes such as 1,3-butadiene. Instantaneous ozone production rates, P(O3), near and downwind of the DPCC ranged from 9 to 24 ppb h−1, which were higher than those over Seoul. Ozone production efficiencies ranged from 6 to 10 downwind of the DPCC and were lower than 10 over Seoul. The contributions of alkenes to the instantaneous secondary organic aerosol (SOA) production rate, P(SOA), were estimated to be comparable to those of more common SOA precursors such as aromatics at intermediate distances from the DPCC. A model case study constrained to an extensive set of observations provided a diagnostic of petrochemical plume chemistry. The simulated plume chemistry reproduced the observed evolution of ozone and short-lived reactive nitrogen compounds, such as PANs and HNs as well as the rate and efficiency of ozone production. The simulated peroxy nitrates (PNs) budget included large contributions (approximately 30%) from unmeasured PNs including peroxyhydroxyacetic nitric anhydride and peroxybenzoic nitric anhydride. The large, predicted levels of these PAN compounds suggest their potential importance in chemical evolution of petrochemical plumes. One unique feature of the DPCC plumes is the substantial contribution of 1,3-butadiene to ozone and potentially SOA production. This work suggests that reductions in small alkene, especially 1,3-butadiene, emissions from the DPCC should be a priority for reducing downwind ozone.

Copyright and License

© 2022 The Author(s). This is an open-access article distributed under the terms of the Creative Commons Attribution 4.0 International License (CC-BY 4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. See http://creativecommons.org/licenses/by/4.0/.

Acknowledgement

The authors would like to thank the KORUS-AQ science team and the DC-8 flight crews.

Funding

YRL, LGH, and DJT acknowledge NASA grant NNX15AT90G and 80NSSC19K1589. DRB, IJS, NJB, and SM acknowledge NASA grant NNX15AT92G. BAN acknowledges NASA grant 80NSSC22K0283. PTR-MS measurements during KORUS-AQ were supported by the Austrian Federal Ministry for Transport, Innovation and Technology (bmvit-FFG-ASAP). PE, LK, and MM supported the PTR-MS measurements. SRH and KU acknowledge NASA grant NNX15AT99G. This work is based upon work supported by the National Center for Atmospheric Research, which is sponsored by the National Science Foundation.

Data Availability

The observational data used in this work are available at: https://doi.org/10.5067/Suborbital/KORUSAQ/DATA01.

Supplemental Material

lee_et_al-202x-si-elementa_science_revised_final_clean- docx file

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elementa.2022.00079.pdf

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Additional details

Related works

Is supplemented by
Dataset: 10.5067/Suborbital/KORUSAQ/DATA01 (DOI)

Funding

National Aeronautics and Space Administration
NNX15AT90G
National Aeronautics and Space Administration
80NSSC19K1589
National Aeronautics and Space Administration
NNX15AT92G
National Aeronautics and Space Administration
80NSSC22K0283
Bundesministerium für Klimaschutz, Umwelt, Energie, Mobilität, Innovation und Technologie
National Aeronautics and Space Administration
NNX15AT99G
NSF National Center for Atmospheric Research

Dates

Accepted
2022-06-03

Caltech Custom Metadata

Caltech groups
Division of Engineering and Applied Science (EAS), Division of Geological and Planetary Sciences (GPS)
Publication Status
Published