Results from the Intergovernmental Panel on Climatic Change Photochemical Model Intercomparison (PhotoComp)

Results from the Intergovernmental Panel on Climatic Change (IPCC) tropospheric photochemical model intercomparison (PhotoComp) are presented with a brief discussion of the factors that may contribute to differences in the modeled behaviors of HOx cycling and the accompanying O3 tendencies. PhotoComp was a tightly controlled model experiment in which the IPCC 1994 assessment sought to determine the consistency among models that are used to predict changes in tropospheric ozone, an important greenhouse gas. Calculated tropospheric photodissociation rates displayed significant differences, with a root-mean-square (rms) error of the reported model results ranging from about ±6-9% of the mean (for O3 and NO2) to up to ±15% (H2O2 and CH2O). Models using multistream methods in radiative transfer calculations showed distinctly higher rates for photodissociation of NO2 and CH2O compared to models using two-stream methods, and this difference accounted for up to one third of the rms error for these two rates. In general, some small but systematic differences between models were noted for the predicted chemical tendencies in cases that did not include reactions of nonmethane hydrocarbons (NMHC). These differences in modeled O3 tendencies in some cases could be identified, for example, as being due to differences in photodissociation rates, but in others they could not and must be ascribed to unidentified errors. O3 tendencies showed rms errors of about ±10% in the moist, surface level cases with NOx concentrations equal to a few tens of parts per trillion by volume. Most of these model to model differences can be traced to differences in the destruction of O3 due to reaction with HO2. Differences in HO2, in turn, are likely due to (1) inconsistent reaction rates used by the models for the conversion of HO2 to H2O2 and (2) differences in the model-calculated photolysis of H2O2 and CH2O. In the middle tropospheric "polluted" scenario with NOx concentrations larger than a few parts per billion by volume, O3 tendencies showed rms errors of ±10-30%. These model to model differences most likely stem from differences in the calculated rates of O3 photolysis to O(1D), which provides about 80% of the HOx source under these conditions. The introduction of hydrocarbons dramatically increased both the rate of NOx loss and its model to model differences, which, in turn, are reflected in an increased spread of predicted O3. Including NMHC in the simulation approximately doubled the rms error for O3 concentration.

Duke Scholars

Author Prasad S. Kasibhatla Environmental Sciences and Policy