Error induced by neglecting subgrid chemical segregation due to inefficient turbulent mixing in regional chemical-transport models in urban environments

In simulations of initially segregated reactive species with an entrainment-emission configuration with an A-B-C second-order chemical scheme, urban surface emission fluxes of the homogeneously emitted tracer A result in a very large segregation between the tracers and hence a very large overestimation of the effective chemical reaction rate in a complete-mixing model.

This large effect can be indicated by a large Damkohler number (Da) of the limiting reactant. With heterogeneous surface emissions of the two reactants, the resultant normalised boundary-layer-averaged effective chemical reaction rate is found to be in a Gaussian function of Da, and it is increasingly overestimated by the imposed rate with an increased horizontal scale of emission heterogeneity. Coarse-grid models with resolutions commensurable to regional models give reduced yet still significant errors for all simulations with homogeneous emissions.