Oxidation of oleic acid at the air-water interface and its potential effects on cloud critical supersaturations

Research output: Contribution to journalArticlepeer-review


  • M.D. King
  • A.R. Rennie
  • K.C. Thompson
  • F.N. Fisher
  • C.C. Dong
  • R.K. Thomas
  • A.V. Hughes

Colleges, School and Institutes


The oxidation of organic films on cloud condensation nuclei has the potential to affect climate and precipitation events. In this work we present a study of the oxidation of a monolayer of deuterated oleic acid (cis-9-octadecenoic acid) at the air–water interface by ozone to determine if oxidation removes the organic film or replaces it with a product film. A range of different aqueous sub-phases were studied. The surface excess of deuterated material was followed by neutron reflection whilst the surface pressure was followed using a Wilhelmy plate. The neutron reflection data reveal that approximately half the organic material remains at the air–water interface following the oxidation of oleic acid by ozone, thus cleavage of the double bond by ozone creates one surface active species and one species that partitions to the bulk (or gas) phase. The most probable products, produced with a yield of ∼(87 ± 14)%, are nonanoic acid, which remains at the interface, and azelaic acid (nonanedioic acid), which dissolves into the bulk solution. We also report a surface bimolecular rate constant for the reaction between ozone and oleic acid of (7.3 ± 0.9) × 10−11 cm2 molecule s−1. The rate constant and product yield are not affected by the solution sub-phase. An uptake coefficient of ozone on the oleic acid monolayer of ∼4 × 10−6 is estimated from our results. A simple Köhler analysis demonstrates that the oxidation of oleic acid by ozone on an atmospheric aerosol will lower the critical supersaturation needed for cloud droplet formation. We calculate an atmospheric chemical lifetime of oleic acid of 1.3 hours, significantly longer than laboratory studies on pure oleic acid particles suggest, but more consistent with field studies reporting oleic acid present in aged atmospheric aerosol.


Original languageEnglish
Pages (from-to)7699-7707
Number of pages9
JournalPhysical Chemistry Chemical Physics
Issue number35
Early online date7 Jul 2009
Publication statusPublished - 21 Sep 2009