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Discussion papers
https://doi.org/10.5194/acp-2019-1168
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-1168
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 16 Jan 2020

Submitted as: research article | 16 Jan 2020

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This preprint is currently under review for the journal ACP.

Impact of NOx on secondary organic aerosol (SOA) formation from α-pinene and β-pinene photo-oxidation: the role of highly oxygenated organic nitrates

Iida Pullinen1,a, Sebastian Schmitt1,b, Sungah Kang1, Mehrnaz Sarrafzadeh1,3,c, Patrick Schlag1,d, Stefanie Andres1, Einhard Kleist2, Thomas F. Mentel1, Franz Rohrer1, Monika Springer1, Ralf Tillmann1, Jürgen Wildt1,2, Cheng Wu1,e, Defeng Zhao1,f, Andreas Wahner1, and Astrid Kiendler-Scharr1 Iida Pullinen et al.
  • 1Institute for Energy and Climate Research, IEK-8, Forschungszentrum Jülich, 52425, Jülich, Germany
  • 2Institute of Bio- and Geosciences, IBG-2, Forschungszentrum Jülich, 52425, Jülich, Germany
  • 3Centre for Atmospheric Chemistry, York University, 4700 Keele St., Toronto, ON M3J 1P3, Canada
  • apresent address: Department of Applied Physics, University of Eastern Finland, Kuopio, Finland
  • bpresent address: TSI GmbH, 52068 Aachen, Germany
  • cpresent address: PerkinElmer, 501 Rowntree Dairy Rd, Woodbridge, ON, L4L 8H1, Canada
  • dpresent address: Shimadzu Deutschland GmbH, 47269 Duisburg, Germany
  • epresent address: Department of Environmental Science, Stockholm University, 11418 Stockholm, Sweden
  • fpresent address: Dept. of Atmos. and Oceanic Sci. & Inst. of Atmos. Sci., Fudan University, Shanghai, 200438, China

Abstract. The formation of organic nitrates (ON) in the gas phase and their impact on mass formation of Secondary Organic Aerosol (SOA) was investigated in a laboratory study for α-pinene and β-pinene photo-oxidation. Focus was the elucidation of those mechanisms that cause the often observed suppression of SOA mass formation by NOx, and therein the role of highly oxygenated multifunctional molecules (HOM). We observed that with increasing NOx (a) the portion of HOM organic nitrates (HOM-ON) increased, (b) the fraction of accretion products (HOM-ACC) decreased and (c) HOM-ACC contained on average smaller carbon numbers.

Specifically, we investigated HOM organic nitrates (HOM-ON), arising from the termination reactions of HOM peroxy radicals with NOx, and HOM permutation products (HOM-PP), such as ketones, alcohols or hydroperoxides, formed by other termination reactions. Effective uptake coefficients γeff of HOM on particles were determined. HOM with more than 6 O-atoms efficiently condensed on particles (γeff > 0.5 in average) and for HOM containing more than 8 O-atoms, every collision led to loss. There was no systematic difference in γeff for HOM-ON and HOM-PP arising from the same HOM peroxy radicals. This similarity is attributed to the multifunctional character of the HOM: as functional groups in HOM arising from the same precursor HOM peroxy radical are identical, vapor pressures should not strongly depend on the character the final termination group. As a consequence, the suppressing effect of NOx on SOA formation cannot be simply explained by replacement of terminal functional groups by organic nitrate groups.

The fraction of organic bound nitrate (OrgNO3) stored in gas-phase HOM-ON appeared to be substantially higher than the fraction of particulate OrgNO3 observed by aerosol mass spectrometry. This result suggests losses of OrgNO3 for organic nitrates in particles, probably due to hydrolysis of OrgNO3 that releases HNO3 into the gas phase but leaves behind the organic rest in the particulate phase. However, the loss of HNO3 alone, could not explain the observed suppressing effect of NOx on particle mass formation from α-pinene and β-pinene.

We therefore attributed most of the reduction in SOA mass yields with increasing NOx to the significant suppression of gas-phase HOM-ACC which have high molecular mass and are potentially important for SOA mass formation at low NOx conditions.

Iida Pullinen et al.

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Short summary
Biogenic and anthropogenic air masses mix in the atmosphere bringing plant emitted monoterpenes and traffic related nitrogen oxides together. There is a debate whether the presence of nitrogen oxides reduces or increases secondary aerosol formation. This is important as secondary aerosols have cooling effects in the climate system but also constitute a health risk in populated areas. We show that the presence of NOx alone should not much affect the mass yields of secondary organic aerosols.
Biogenic and anthropogenic air masses mix in the atmosphere bringing plant emitted monoterpenes...
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