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- Title
Experimental investigation into the volatilities of highly oxygenated organic molecules (HOM).
- Authors
Peräkylä, Otso; Riva, Matthieu; Heikkinen, Liine; Quéléver, Lauriane; Roldin, Pontus; Ehn, Mikael
- Abstract
Secondary organic aerosol (SOA) forms a major part of the tropospheric submicron aerosol. Still, the exact formation mechanisms of SOA have remained elusive. Recently, a newly discovered group of oxidation products of volatile organic compounds (VOC), highly oxygenated organic molecules (HOM), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOM to form SOA, and to even take part in new particle formation, knowledge of their exact volatilities would be essential. However, due to their exotic, and partially unknown, structures, estimating their volatility is challenging. In this study, we performed a set of continuous flow chamber experiments, supported by box modelling, to study the volatilities of HOM, along with some less oxygenated compounds, formed in the ozonolysis of alpha-pinene, an abundant VOC emitted by the boreal forests. Along with gaseous precursors, we periodically injected inorganic seed aerosol into the chamber to vary the condensation sink (CS) of low volatility vapours. We monitored the decrease of oxidation products in the gas phase in response to increasing CS, and were able to relate the responses to the volatilities of the compounds. We found that HOM monomers are mainly of low volatility, with a small fraction being semi-volatile. HOM dimers were all of at least low volatility, but probably of extremely low volatility: however, our method is not directly able to distinguish between the two. We were able to explain the volatility of the oxidation products in terms of their carbon, hydrogen, oxygen and nitrogen numbers. We found that increasing levels of oxygenation correspond to lower volatilities, as expected, but that the decrease is less steep than would be expected based on many existing models for volatility, such as SIMPOL. The hydrogen number of a compound also explained its volatility, independently of the carbon number, with higher hydrogen numbers corresponding to lower volatilities. This can be explained in terms of the functional groups making up a molecule: high hydrogen numbers are associated with e.g. hyrdoxy groups, which lower the volatility more than e.g. carbonyls, that are associated with a lower hydrogen number. The method presented should be applicable to systems other than α-pinene ozonolysis, and with different organic loadings in order to study different volatility ranges.
- Subjects
PINENE; TROPOSPHERIC aerosols; TAIGAS; MONOMERS; VOLATILE organic compounds; MOLECULES
- Publication
Atmospheric Chemistry & Physics Discussions, 2019, p1
- ISSN
1680-7367
- Publication type
Article
- DOI
10.5194/acp-2019-620