The importance of sesquiterpene oxidation products for secondary organic aerosol formation in a springtime hemiboreal forest

Secondary organic aerosols (SOAs) formed from biogenic volatile organic compounds (BVOCs) constitute a significant fraction of atmospheric particulate matter and have been recognized to significantly affect the climate and air quality. Atmospheric SOA particulate mass yields and chemical composition result from a complex mixture of oxidation products originating from a diversity of BVOCs. Many laboratory and field experiments have studied SOA particle formation and growth in the recent years. However, a large uncertainty still remains regarding the contribution of BVOCs to SOA. In particular, organic compounds formed from sesquiterpenes have not been thoroughly investigated, and their contribution to SOA remains poorly characterized. In this study, a Filter Inlet for Gases and Aerosols (FI-GAERO) combined with a high-resolution time-of-flight chemical ionization mass spectrometer (CIMS), with iodide ionization, was used for the simultaneous measurement of gas-phase and particle-phase oxygenated compounds. The aim of the study was to evaluate the relative contribution of sesquiterpene oxidation products to SOA in a springtime hemiboreal forest environment. Our results revealed that monoterpene and sesquiterpene oxidation products were the main contributors to SOA particles. The chemical composition of SOA particles was compared for times when either monoterpene or sesquiterpene oxidation products were dominant and possible key oxidation products for SOA particle formation were identified for both situations. Surprisingly, sesquiterpene oxidation products were the predominant fraction in the particle phase in some periods, while their gas-phase concentrations remained much lower than those of monoterpene products. This can be explained by favorable and effective partitioning of sesquiterpene products into the particle phase. The SOA particle volatility determined from measured thermograms increased when the concentration of sesquiterpene oxidation products in SOA particles was higher than that of monoterpenes. Overall, this study demonstrates that sesquiterpenes may have an important role in atmospheric SOA formation and oxidation chemistry, in particular during the spring recovery period.

Automated summary

This study used a combination of a Filter Inlet for Gases and Aerosols (FI-GAERO) and a high-resolution time-of-flight chemical ionization mass spectrometer (CIMS) with iodide ionization to evaluate the relative contribution of sesquiterpene oxidation products to SOA in a springtime hemiboreal forest environment. The results showed that both monoterpene and sesquiterpene oxidation products were major contributors to SOA particles, indicating that sesquiterpenes may play an important role in atmospheric SOA formation and oxidation chemistry, especially during the spring recovery period.