A scaling analysis of ozone photochemistry

Abstract

Abstract. A scaling analysis has been used to capture the integrated behaviour of several photochemical mechanisms for a wide range of precursor concentrations and a variety of environmental conditions. The Buckingham Pi method of dimensional analysis was used to express the relevant variables in terms of dimensionless groups. These grouping show maximum ozone, initial NOx and initial VOC concentrations are made non-dimensional by the average NO2 photolysis rate (jav) and the rate constant for the NO–O3 titration reaction (kNO); temperature by the NO–O3 activation energy (ENO) and Boltzmann constant (k) and total irradiation time by the cumulative javΔt photolysis rate. The analysis shows dimensionless maximum ozone concentration can be described by a product of powers of dimensionless initial NOx concentration, dimensionless temperature, and a similarity curve directly dependent on the ratio of initial VOC to NOx concentration and implicitly dependent on the cumulative NO2 photolysis rate. When Weibull transformed, the similarity relationship shows a scaling break with dimensionless model output clustering onto two straight line segments, parameterized using four variables: two describing the slopes of the line segments and two giving the location of their intersection. A fifth parameter is used to normalize the model output. The scaling analysis, similarity curve and parameterization appear to be independent of the details of the chemical mechanism, hold for a variety of VOC species and mixtures and a wide range of temperatures and actinic fluxes.