15 Jul 2021

15 Jul 2021

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

Secondary Organic Aerosol Formation from Camphene Oxidation: Measurements and Modeling

Qi Li1,2, Jia Jiang1,2, Isaac Afreh1,2, Kelley C. Barsanti1,2, and David R. Cocker III1,2 Qi Li et al.
  • 1Department of Chemical and Environmental Engineering, University of California-Riverside, Riverside, California 92521, United States
  • 2The Bourns College of Engineering, Center for Environmental Research and Technology, University of California- Riverside, Riverside, California 92507, United States

Abstract. While camphene is one of the dominant monoterpenes measured in biogenic and biomass burning emission samples, oxidation of camphene has not been well-studied in environmental chambers and very little is known about its potential to form secondary organic aerosol (SOA). The lack of chamber-derived SOA data for camphene may lead to significant uncertainties in predictions of SOA from oxidation of monoterpenes using existing parameterizations when camphene is a significant contributor to total monoterpenes. Therefore, to advance the understanding of camphene oxidation and SOA formation, and to improve representation of camphene in air quality models, a series of experiments were performed in the University of California Riverside environmental chamber to explore camphene SOA yields and properties across a range of chemical conditions at atmospherically relevant OH concentrations. The experimental results were compared with modeling simulations obtained using two chemically detailed box models, Statewide Air Pollution Research Center (SAPRC) and Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). SOA parameterizations were derived from the chamber data using both the two-product and volatility basis set (VBS) approaches. Experiments performed with added nitrogen oxides (NOx) resulted in higher SOA yields (up to 64 %) than experiments performed without added NOx (up to 28 %). In addition, camphene SOA yields increased with SOA mass (Mo) at lower mass loadings, but a threshold was reached at higher mass loadings in which the SOA yields no longer increased with Mo. SAPRC modeling of the chamber studies suggested that the higher SOA yields at higher initial NOx levels were primarily due to higher production of peroxy radicals (RO2) and the generation of highly oxygenated organic molecules (HOMs) formed through unimolecular RO2 reactions. SAPRC predicted that in the presence of NOx, camphene RO2 reacts with NO and the resultant RO2 undergo hydrogen (H)-shift isomerization reactions; as has been documented previously, such reactions rapidly add oxygen and lead to products with very low volatility (i.e., HOMs). The end products formed in the presence of NOx have significantly lower volatilities, and higher O : C ratios, than those formed by initial camphene RO2 reacting with hydroperoxyl radicals (HO2) or other RO2. Moreover, particle densities were found to decrease from 1.47 to 1.30 g cm−3 as [HC]0/[NOx]0 increased and O : C decreased. The observed differences in SOA yields were largely explained by the gas-phase RO2 chemistry and the competition between RO2 + HO2, RO2 + NO, RO2 + RO2, and RO2 unimolecular reactions.

Qi Li et al.

Status: open (until 26 Aug 2021)

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Qi Li et al.


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Short summary
The chamber-derived SOA yields from camphene are reported for the first time. The role of peroxy radicals (RO2) was investigated using chemically detailed box models. We observed higher SOA yields (up to 64 %) in the experiments with added NOx than without, due to the formation of highly oxygenated organic molecules (HOMs) when NOx is present. This work can improve the representation of camphene in air quality models and provide insights into other monoterpene studies.