4.8 Article

Photo-oxidation of Aromatic Hydrocarbons Produces Low-Volatility Organic Compounds

Journal

ENVIRONMENTAL SCIENCE & TECHNOLOGY
Volume 54, Issue 13, Pages 7911-7921

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.est.0c02100

Keywords

-

Funding

  1. European Organization for Nuclear Research (CERN)
  2. U.S. National Science Foundation [AGS-1447056, AGS-1439551, AGS-1649147, AGS-1602086, AGS-1801897]
  3. German Federal Ministry of Education and Research [01LK1601A]
  4. ERC-Consolidator [NANO-DYNAMITE 616075]
  5. Horizon 2020 Marie Sklodowska-Curie Grant [656994]
  6. ERC Advanced ATM-GP grant [227463]
  7. Presidium of the Russian Academy of Sciences
  8. Swiss National Science Foundation [200020_152907, 20FI20_159851, 200021_169090, 200020_172602, 20FI20_172622]
  9. MRI grant [AGS-1531284]
  10. Wallace Research Foundation
  11. Doctoral Programme in Atmospheric Sciences at the University of Helsinki
  12. Swiss National Science Foundation (SNF) [200020_172602, 20FI20_159851, 20FI20_172622, 200020_152907] Funding Source: Swiss National Science Foundation (SNF)

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To better understand the role of aromatic hydrocarbons in new-particle formation, we measured the particle-phase abundance and volatility of oxidation products following the reaction of aromatic hydrocarbons with OH radicals. For this we used thermal desorption in an iodide-adduct Time-of-Flight Chemical-Ionization Mass Spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-ToF-CIMS). The particle-phase volatility measurements confirm that oxidation products of toluene and naphthalene can contribute to the initial growth of newly formed particles. Toluene-derived (C-7) oxidation products have a similar volatility distribution to that of alpha-pinene-derived (C-10) oxidation products, while naphthalene-derived (C-10) oxidation products are much less volatile than those from toluene or alpha-pinene; they are thus stronger contributors to growth. Rapid progression through multiple generations of oxidation is more pronounced in toluene and naphthalene than in alpha-pinene, resulting in more oxidation but also favoring functional groups with much lower volatility per added oxygen atom, such as hydroxyl and carboxylic groups instead of hydroperoxide groups. Under conditions typical of polluted urban settings, naphthalene may well contribute to nucleation and the growth of the smallest particles, whereas the more abundant alkyl benzenes may overtake naphthalene once the particles have grown beyond the point where the Kelvin effect strongly influences the condensation driving force.

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