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Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)833-842
Number of pages10
JournalACS Earth and Space Chemistry
Volume2
Issue number8
Early online date26 Jun 2018
DOIs
DateAccepted/In press - 26 Jun 2018
DateE-pub ahead of print - 26 Jun 2018
DatePublished (current) - 16 Aug 2018

Abstract

Trace atmospheric concentrations of carboxylic acids have a potent effect upon the environment, where they modulate aqueous chemistry and perturb Earth’s radiative balance. Halogenated carboxylic acids are produced by the tropospheric oxidation of halocarbons and are considered persistent pollutants because of their weak tropospheric and aqueous sinks. However, recent studies reported rapid reactions between selected carboxylic acids and Criegee intermediates, which may provide an efficient gas-phase removal process. Accordingly, absolute rate coefficients of two Criegee intermediates, CH2OO and (CH3)2COO, with a suite of carboxylic acids (HCOOH, CH3COOH, CClF2COOH, CF3CF2COOH, and pyruvic acid) were measured with a view to develop a structure-activity relationship (SAR). This SAR is based upon the dipole-capture model and predicts the reactivity of many further combinations of Criegee intermediates and carboxylic acids. Complementary synchrotron-based photoionization mass spectrometry measurements demonstrate that these reactions produce stable ester adducts, with a reaction coordinate involving transfer of the acidic hydrogen from the carboxylic acid to the terminal oxygen of the Criegee intermediate. The adduct products are predicted to have low vapour pressures, and coupling of this chemistry with a global atmospheric chemistry and transport model shows significant production of secondary organic aerosol at locations rich in biogenic alkene emissions.

    Research areas

  • Atmospheric Chemistry, Carboxylic Acids, Criegee Intermediate, Hydroperoxide Ester;, SOA

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  • Full-text PDF (accepted author manuscript)

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via ACS at https://pubs.acs.org/doi/10.1021/acsearthspacechem.8b00069 . Please refer to any applicable terms of use of the publisher.

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    Embargo ends: 26/06/19

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