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Experimental investigation into the volatilities of highly oxygenated organic molecules (HOMs)

Peräkylä, Otso ; Riva, Matthieu ; Heikkinen, Liine ; Quéléver, Lauriane ; Roldin, Pontus LU and Ehn, Mikael (2020) In Atmospheric Chemistry and Physics 20(2). p.649-669
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 (VOCs), highly oxygenated organic molecules (HOMs), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOMs to form SOA and to even take part in new particle formation, knowledge of their exact volatilities is 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... (More)

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 (VOCs), highly oxygenated organic molecules (HOMs), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOMs to form SOA and to even take part in new particle formation, knowledge of their exact volatilities is 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 HOMs, along with some less oxygenated compounds, formed in the ozonolysis of a-pinene, an abundant VOC emitted by 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 at least low volatility, but probably extremely low volatility; however, our method is not directly able to distinguish between the two. We were able to model 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 predicted 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. hydroxy groups, which lower volatility more than, e.g. carbonyls, which are associated with a lower hydrogen number. The method presented should be applicable to systems other than a-pinene ozonolysis, and with different organic loadings, in order to study different volatility ranges.

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type
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published
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in
Atmospheric Chemistry and Physics
volume
20
issue
2
pages
21 pages
publisher
Copernicus Gesellschaft mbH
external identifiers
  • scopus:85078436170
ISSN
1680-7316
DOI
10.5194/acp-20-649-2020
language
English
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yes
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9d87c3bf-b651-40d4-91d3-97d9dc7c8e5e
date added to LUP
2020-02-07 13:42:32
date last changed
2020-05-24 06:29:38
@article{9d87c3bf-b651-40d4-91d3-97d9dc7c8e5e,
  abstract     = {<p>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 (VOCs), highly oxygenated organic molecules (HOMs), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOMs to form SOA and to even take part in new particle formation, knowledge of their exact volatilities is 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 HOMs, along with some less oxygenated compounds, formed in the ozonolysis of a-pinene, an abundant VOC emitted by 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 at least low volatility, but probably extremely low volatility; however, our method is not directly able to distinguish between the two. We were able to model 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 predicted 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. hydroxy groups, which lower volatility more than, e.g. carbonyls, which are associated with a lower hydrogen number. The method presented should be applicable to systems other than a-pinene ozonolysis, and with different organic loadings, in order to study different volatility ranges.</p>},
  author       = {Peräkylä, Otso and Riva, Matthieu and Heikkinen, Liine and Quéléver, Lauriane and Roldin, Pontus and Ehn, Mikael},
  issn         = {1680-7316},
  language     = {eng},
  number       = {2},
  pages        = {649--669},
  publisher    = {Copernicus Gesellschaft mbH},
  series       = {Atmospheric Chemistry and Physics},
  title        = {Experimental investigation into the volatilities of highly oxygenated organic molecules (HOMs)},
  url          = {http://dx.doi.org/10.5194/acp-20-649-2020},
  doi          = {10.5194/acp-20-649-2020},
  volume       = {20},
  year         = {2020},
}