Effects of turbulence and heterogeneous emissions on photochemically active species in the convective boundary layer

Abstract

Photochemistry is studied in a convective atmospheric boundary layer. The essential reactions that account for the ozone formation and depletion are included in the chemical mechanism which, as a consequence, contains a wide range of timescales. The turbulent reacting flow is modeled with a large‐eddy simulation (LES) code. The deviations from chemical equilibrium that are caused by turbulent motions are investigated in terms of the intensity of segregation. For the studied cases it is found that the volume‐averaged concentrations calculated with the LES code agree well with the concentrations calculated with a box model. The reaction rate between RH (a generic hydrocarbon emitted at the surface) and OH is most strongly affected (3% slower than in the box model). However, if RH is emitted nonuniformly at the surface, or if the RH‐OH reaction rate is increased, the volume‐averaged RH destruction by OH may be slowed down by as much as 30% compared to a box model. Sensitivity studies showed that the intensity of segregation between RH and OH not only depends on the strength and spatial distribution of the RH emissions but also on the way NO is emitted in the model atmosphere. The results obtained indicate that the assumption that localized emissions of reactive hydrocarbons, for example, isoprene or terpenes, are instantaneously mixed may lead to an underestimation of their atmospheric lifetime.