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.

Highlights

  • On a global scale, biogenic monoterpene emissions are estimated to contribute 14% of the total reactive volatile organic compounds (VOC) flux (Guenther, 1995)

  • While camphene is one of the dominant monoterpenes measured in biogenic and biomass burning emission 10 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)

  • 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

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Summary

Introduction

Biogenic monoterpene emissions are estimated to contribute 14% of the total reactive volatile organic compounds (VOC) flux (Guenther, 1995). NOx levels influence the amount of SOA produced in the initial oxidation steps by controlling the relative proportions of oxidants, the fractional reactivity with 75 those oxidants, and the volatility distribution of the products formed (Hurley et al, 2001; Nøjgaard et al, 2006; Kroll and Seinfeld, 2008). Previous studies of relatively small compounds (carbon number 10), including monoterpenes such as α-pinene, have reported that SOA yields generally increase as initial NOx decreases, with a proposed mechanism of competitive chemistry between RO2 + HO2 and RO2 + NO pathways, of which the latter would form more volatile products (Kroll et al, 2006; Ng et al, 2007; Song et al, 2005). We present the first systematic study of SOA formation from camphene using laboratory-based chamber experiments and chemically detailed box models. 90 Organics in the Atmosphere (GECKO-A), were used to provide mechanistic insights into the chamber observations and to elucidate the connections between the fate of RO2 and camphene SOA formation

Chamber Facility and Instrumentation
Experimental Conditions
Model Configurations and Conditions
Discussion
Camphene + OH Gas-phase Mechanism
The Formation of HOMs and Influence on SOA Yields
GECKO-A simulations
Conclusions
Findings
470 Acknowledgements

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