Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS)

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.