Emerging investigator series: secondary organic aerosol formation from photooxidation of acyclic terpenes in an oxidation flow reactor.

Abstract

One major challenge in predicting secondary organic aerosol (SOA) formation in the atmosphere is incomplete representation of biogenic volatile organic compounds (BVOCs) emitted from plants, particularly those that are emitted as a result of stress - a condition that is becoming more frequent in a rapidly changing climate. One of the most common types of BVOCs emitted by plants in response to environmental stress are acyclic terpenes. In this work, SOA is generated from the photooxidation of acyclic terpenes in an oxidation flow reactor and compared to SOA production from a reference cyclic terpene - α-pinene. The acyclic terpenes used as SOA precursors included β-myrcene, β-ocimene, and linalool. Results showed that oxidation of all acyclic terpenes had lower SOA yields measured after 4 days photochemical age, in comparison to α-pinene. However, there was also evidence that the condensed organic products that formed, while a smaller amount overall, had a higher oligomeric content. In particular, β-ocimene SOA had higher oligomeric content than all the other chemical systems studied. SOA composition data from ultra-high performance liquid chromatography with electrospray ionization mass spectrometry (UHPLC-ESI-MS) was combined with mechanistic modeling using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to explore chemical mechanisms that could lead to this oligomer formation. Calculations based on composition data suggested that β-ocimene SOA was more viscous with a higher glass transition temperature than other SOA generated from acyclic terpene oxidation. This was attributed to a higher oligomeric content compared to other SOA systems studied. These results contribute to novel chemical insights about SOA formation from acyclic terpenes and relevant chemistry processes, highlighting the importance of improving underrepresented biogenic SOA formation in chemical transport models.