1The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, M13 9PL, UK
2Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS, UK
3Centre for Atmospheric Science, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK
4Atmospheric Chemistry Services, Okehampton, Devon, EX20 1FB, UK
5rdscientific, Newbury, Berkshire, UK
*current address: Chemical Sciences Division, Earth System Research Laboratory, National Oceanic and Atmospheric Administration (NOAA), 325 Broadway, Boulder, CO 80305, USA
Received: 19 Jul 2011 – Discussion started: 09 Sep 2011
Abstract. Gas-phase ethene ozonolysis experiments were conducted at room temperature to determine formic acid yields as a function of relative humidity (RH) using the integrated EXTreme RAnge chamber-Chemical Ionisation Mass Spectrometry technique, employing a CH3I ionisation scheme. RHs studied were <1, 11, 21, 27, 30 % and formic acid yields of (0.07±0.01) and (0.41±0.07) were determined at <1 % RH and 30 % RH respectively, showing a strong water dependence. It has been possible to estimate the ratio of the rate coefficient for the reaction of the Criegee biradical, CH2OO with water compared with decomposition. This analysis suggests that the rate of reaction with water ranges between 1×10−12–1×10−15 cm3 molecule−1 s−1 and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Global model integrations suggest that this reaction between CH2OO and water may dominate the production of HC(O)OH in the atmosphere.
Revised: 02 Dec 2011 – Accepted: 08 Dec 2011 – Published: 09 Jan 2012
Leather, K. E., McGillen, M. R., Cooke, M. C., Utembe, S. R., Archibald, A. T., Jenkin, M. E., Derwent, R. G., Shallcross, D. E., and Percival, C. J.: Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS), Atmos. Chem. Phys., 12, 469-479, doi:10.5194/acp-12-469-2012, 2012.