Articles | Volume 8, issue 21
Atmos. Chem. Phys., 8, 6453–6468, 2008
Atmos. Chem. Phys., 8, 6453–6468, 2008

  13 Nov 2008

13 Nov 2008

Evaluation of 1,3,5 trimethylbenzene degradation in the detailed tropospheric chemistry mechanism, MCMv3.1, using environmental chamber data

A. Metzger1, J. Dommen1, K. Gaeggeler1, J. Duplissy1, A. S. H. Prevot1, J. Kleffmann2, Y. Elshorbany2, A. Wisthaler3, and U. Baltensperger1 A. Metzger et al.
  • 1Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen, Switzerland
  • 2Physikalische Chemie/FB C, Bergische Universität Wuppertal, 42097 Wuppertal, Germany
  • 3Institut für Ionenphysik, Universität Innsbruck, 6020 Innsbruck, Austria

Abstract. The degradation mechanism of 1,3,5-trimethyl- benzene (TMB) as implemented in the Master Chemical Mechanism version 3.1 (MCM) was evaluated using data from the environmental chamber at the Paul Scherrer Institute. The results show that the MCM provides a consistent description of the photo-oxidation of TMB/NOx mixtures for a range of conditions. In all cases the agreement between the measurement and the simulation decreases with decreasing VOC-NOx ratio and in addition with increasing precursor concentration. A significant underestimation of the decay rate of TMB and thus underestimation of reactivity in the system, consistent with results from previous appraisals of the MCM, was observed.

Much higher nitrous acid (HONO) concentrations compared to simulations and expected from chamber characterization experiments were measured during these smog chamber experiments. A light induced NO2 to HONO conversion at the chamber walls is suggested to occur. This photo-enhanced NO2 to HONO conversion with subsequent HONO photolysis enhances the reactivity of the system. After the implementation of this reaction in the model it describes the decay of TMB properly. Nevertheless, the model still over-predicts ozone at a later stage of the experiment. This can be attributed to a too slow removal of NO2. It is also shown that this photo-enhanced HONO formation is not restricted to TMB photo-oxidation but also occurs in other chemical systems (e.g. α-pinene). However, the influence of HONO as a source of OH radicals is less important in these more reactive systems and therefore the importance of the HONO chemistry is less obvious.

Final-revised paper