Contrasting impacts of humidity on the ozonolysis of monoterpenes: insights into the multi-generation chemical mechanism

Abstract. Secondary organic aerosol (SOA) formed from the ozonolysis of biogenic monoterpenes is a major source of atmospheric organic aerosol. It has been previously found that relative humidity (RH) can influence the SOA formation from some monoterpenes, yet most studies only observed the increase or decrease in SOA yield without further explanations of molecular-level mechanisms. In this study, we chose two structurally different monoterpenes (limonene with an endocyclic double bond and an exocyclic double bond, Δ3-carene with only an endocyclic double bond) to investigate the effect of RH in a set of oxidation flow reactor experiments. We find contrasting impacts of RH on the SOA formation: limonene SOA yield increases by ∼100 % as RH increases, while there is a slight decrease in Δ3-carene SOA yield. Although the complex processes in the particle phase may play a role, we primarily attribute the results to the water-influenced reactions after ozone attack on the exocyclic double bond of limonene, which leads to the increment of lower volatile organic compounds under high-RH conditions. However, as Δ3-carene only has an endocyclic double bond, it cannot undergo such reactions. This hypothesis is further supported by the SOA yield enhancement of β-caryophyllene, a sesquiterpene that also has an exocyclic double bond. These results greatly improve our understanding of how water vapor influences the ozonolysis of biogenic organic compounds and subsequent SOA formation processes.