• Open Access

Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications

Authors

  • Dr. Oliver Welz,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. Arkke J. Eskola,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. Leonid Sheps,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. Brandon Rotavera,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. John D. Savee,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. Adam M. Scheer,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. David L. Osborn,

    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
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  • Dr. Douglas Lowe,

    1. The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL (UK)
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  • Dr.  A. Murray Booth,

    1. The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL (UK)
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  • Ping Xiao,

    1. Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS (UK)
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  • Dr.  M. Anwar H. Khan,

    1. Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS (UK)
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  • Prof. Carl J. Percival,

    Corresponding author
    1. The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL (UK)
    • Carl J. Percival, The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL (UK)===

      Dudley E. Shallcross, Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS (UK)===

      Craig A. Taatjes, Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)===

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  • Prof. Dudley E. Shallcross,

    Corresponding author
    1. Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS (UK)
    • Carl J. Percival, The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL (UK)===

      Dudley E. Shallcross, Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS (UK)===

      Craig A. Taatjes, Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)===

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  • Dr. Craig A. Taatjes

    Corresponding author
    1. Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)
    • Carl J. Percival, The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL (UK)===

      Dudley E. Shallcross, Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS (UK)===

      Craig A. Taatjes, Combustion Research Facility, Sandia National Laboratories, Stop 9055, Livermore, CA 94551-0969 (USA)===

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  • We thank Howard Johnsen and the staff at the Chemical Dynamics Beamline for technical support of the MPIMS experiments. Sandia authors and the development and maintenance of the MPIMS experiment, were funded by the Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Sciences (BES), United States Department of Energy (DOE). Development of the time-resolved broadband cavity-enhanced absorption spectrometer was supported by the Laboratory Directed Research and Development program at Sandia National Laboratories. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration, under contract DE-AC04-94AL85000. The Advanced Light Source is supported by the Director, Office of Science, BES/DOE, under contract DE-AC02-05CH11231 between Lawrence Berkeley National Laboratory and the DOE. C.J.P. and D.E.S. thank NERC under whose auspices some aspects of this work were carried out.

Abstract

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2OO and CH3CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10−10 cm3 s−1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.

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