Issue 7, 2024

Kinetic study of isoprene hydroxy hydroperoxide radicals reacting with sulphur dioxide and their global-scale impact on sulphate formation

Abstract

Isoprene is the most relevant volatile organic compound emitted during the biosynthesis of metabolism processes. The oxidation of isoprene by a hydroxy radical (OH) is one of the main consumption schemes that generate six isomers of isoprene hydroxy hydroperoxide radicals (ISOPOOs). In this study, the rate constants of ISOPOOs + sulphur dioxide (SO2) reactions that eventually generate sulphur trioxide (SO3), the precursor of sulphate aerosol (SO42−(p)), are determined using microcanonical kinetic theories coupled with molecular structures and energies estimated by quantum chemical calculations. The results show that the reaction rates range from 10−27 to 10−20 cm3 molecule−1 s−1, depending on the atmospheric temperature and structure of the six ISOPOO isomers. The effect of SO3 formation from SO2 oxidation by ISOPOOs on the atmosphere is evaluated by a global chemical transport model, along with the rate constants obtained from microcanonical kinetic theories. The results show that SO3 formation is enhanced in regions with high SO2 or low nitrogen oxide (NO), such as China, the Middle East, and Amazon rainforests. However, the production rates of SO3 formation by ISOPOOs + SO2 reactions are eight orders of magnitude lower than that from the OH + SO2 reaction. This is indicative of SO42−(p) formation from the direct oxidation of SO2 by ISOPOOs, which is almost negligible in the atmosphere. The results of this study entail a detailed analysis of SO3 formation from gas-phase reactions of isoprene-derived products.

Graphical abstract: Kinetic study of isoprene hydroxy hydroperoxide radicals reacting with sulphur dioxide and their global-scale impact on sulphate formation

Supplementary files

Article information

Article type
Paper
Submitted
25 apr 2024
Accepted
21 mei 2024
First published
10 jun 2024
This article is Open Access
Creative Commons BY license

Environ. Sci.: Processes Impacts, 2024,26, 1147-1155

Kinetic study of isoprene hydroxy hydroperoxide radicals reacting with sulphur dioxide and their global-scale impact on sulphate formation

H. Hata and K. Tonokura, Environ. Sci.: Processes Impacts, 2024, 26, 1147 DOI: 10.1039/D4EM00232F

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