Physical Sciences Division
Published June 24, 2024 | Version v1
Journal article Open

Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set

Creators

  • 1. Carnegie Mellon University
  • 2. Goethe University Frankfurt
  • 3. TU Wien
  • 4. Paul Scherer Institute
  • 5. University of Chicago
  • 6. National Science Foundation
  • 7. University of Helsinki
  • 8. University of Vienna
  • 9. University of Colorado Boulder
  • 10. Lebedev Fisysical Institute
  • 11. Pusan National University

Description

Isoprene affects new particle formation rates in environments and experiments also containing monoterpenes. For the most part, isoprene reduces particle formation rates, but the reason is debated. It is proposed that due to its fast reaction with OH, isoprene may compete with larger monoterpenes for oxidants. However, by forming a large amount of peroxy-radicals (RO2), isoprene may also interfere with the formation of the nucleating species compared to a purely monoterpene system. We explore the RO2 cross reactions between monoterpene and isoprene oxidation products using the radical Volatility Basis Set (radical-VBS), a simplified reaction mechanism, comparing with observations from the CLOUD experiment at CERN. We find that isoprene interferes with covalently bound C20 dimers formed in the pure monoterpene system and consequently reduces the yields of the lowest volatility (Ultra Low Volatility Organic Carbon, ULVOC) VBS products. This in turn reduces nucleation rates, while having less of an effect on subsequent growth rates.

Notes

Due to the large number of authors, only the first 20 and the University of Chicago authors are included on the above author list. Please download the article for the complete list of authors.

Data availability

The data unique to this work are the rate coefficients and reaction sequence contained in the ESI.

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Additional details

Identifiers

DOI
10.1039/D4EA00056K
Other
oai:uchicago.tind.io:14479

Funding

National Science Foundation
CHE2336463
Vienna Science and Technology Fund
VRG22-003
Swiss National Science Foundation
PZ00P2_216181
Swiss National Foundation
200021_213071
European Research Council
ERC 616075

UChicago Information

Division(s)
Physical Sciences Division
Department(s)
Geophysical Sciences