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- Title
SIZE DEPENDENT CHEMICAL AGEING OF OLEIC ACID AEROSOL UNDER DRY AND HUMIDIFIED CONDITIONS.
- Authors
Al-Kindi, Suad; Pope, Francis D.; Beddows, David C.; Bloss, William J.; Harrison, Roy M.
- Abstract
A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65% R.H.. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azaleic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid, and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 μm diameter) and relative humidity. Under dry conditions, the percentage residual oleic acid increases with increasing particle size, as does the percentage of higher molecular weight products, due to the poorer internal mixing of the larger particles. The main lower molecular weight products are nonanal and oxonononic acid. Under humidified conditions, the percentage unreacted oleic acid is greater, except in the smallest particle fraction, and oxononanoic acid dominates the product distribution, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the oleic acid model aerosol system is of limited relevance to complex internally mixed atmospheric aerosol, the generic findings presented in this paper give useful insights into the nature of heterogeneous chemical processes.
- Subjects
OLEIC acid; CHEMICAL reactions; ATMOSPHERIC aerosols; OZONOLYSIS; TIME-of-flight mass spectrometry
- Publication
Atmospheric Chemistry & Physics Discussions, 2016, p1
- ISSN
1680-7367
- Publication type
Article
- DOI
10.5194/acp-2016-230