Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published October 3, 2019 | Published + Supplemental Material
Journal Article Open

Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles


α-Hydroxyalkyl-hydroperoxides (α-HHs), from the addition of water to Criegee intermediates in the ozonolysis of olefins, are reactive components of organic aerosols. Assessing the fate of α-HHs in such media requires information on the rates and products of their reactions in aqueous organic matrices. This information, however, is unavailable due to the lack of analytical techniques for the detection and identification of labile α-HHs. Here, we report the mass spectrometric detection (as Cl- adducts) of the α-HH produced in the ozonolysis of a C_(15) diolefin in water (W):acetonitrile (AN) mixtures of variable composition. α-HH decays into a gem-diol + H_2O_2 in τ_(1/e) ~ 52 min in 50% (v:v) water, but persists longer than a day in < 10% water mixtures. The strong non-linear dependence of τ_(1/e) on water content reveals that water content is a major factor controlling the fate of α-HHs in atmospheric particles, and suggests that α-HH decomposes while embedded in W_nAN_m clusters rather than randomly dissolved in molecularly homogeneous W:AN mixtures.

Additional Information

© 2019 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: July 6, 2019; Accepted: September 9, 2019; Published: September 9, 2019. S. E. is grateful to the JSPS KAKENHI grant number 15H05328 and 19H01154. A.J.C. acknowledges support from the National Science Foundation USA, grant AGS-1744353. Author Contributions: S.E. designed research; J.Q. and S.E. performed experiments; S.E. contributed new reagents/analytic tools. All authors analyzed data and wrote the paper.

Attached Files

Published - acs.jpclett.9b01953.pdf

Supplemental Material - jz9b01953_si_001.pdf


Files (1.7 MB)
Name Size Download all
229.1 kB Preview Download
1.5 MB Preview Download

Additional details

August 19, 2023
October 18, 2023