Pressure dependent aerosol formation from the cyclohexene gas-phase ozonolysis in the presence and absence of sulfur dioxide: a new perspective on the stabilisation of the initial clusters

Abstract

The ozonolysis of cyclohexene is studied with respect to the pressure dependent formation of stable gas-phase products and secondary organic aerosol (SOA) as well as the influence of the presence of SO₂. In addition the rate coefficient for the initial reaction cyclohexene + O₃ was determined at 295 K. The observed increase in CO and ethene yields at low pressures and the absence of ketene in the product spectrum confirm previously proposed reaction pathways forming these decomposition products. An enhanced ethene formation at pressures below 300 mbar coincides with drastically decreased aerosol yields pointing to a high influence on SOA formation of chemical activation driven dynamics in the vinylhydroperoxide channel. The static reactor experiments at 450 mbar in the presence of SO₂ in the present study showed a similar sensitivity of additional particle formation to H₂SO₄ number densities as found in near-atmospheric flow reactor experiments [Sipilä et al., Science, 2010, 327, 1243], a surprising result with regard to the very different experimental approaches. At low pressures (around 40 mbar) no significant new particle formation is observed even at high H₂SO₄ concentrations. These findings indicate that the collisional stabilisation of initial clusters is an important aspect for SOA formation processes involving sulfuric acid and organic compounds. The results may have implications for geo-engineering strategies based on stratospheric sulfur injection, but caution is mandatory when room temperature laboratory results are extrapolated to stratospheric conditions.