Abstract
A detailed photochemical mechanism for the atmospheric reactions of isoprene and its major oxidation products in the presence of NOx, which incorporates the most recent laboratory results and our current understanding of the system, is described. It is evaluated by comparing its predictions against results of NOx-air irradiations of isoprene and its two major products, methacrolein, and methyl vinyl ketone (MVK), in five different types of environmental chambers at two different laboratories. In most cases it simulated experimental results within the uncertainty of the data and the chamber and run characterization model. However, the photodecomposition quantum yields of methacrolein and MVK and the organic nitrate yield from the OH + isoprene reaction had to be adjusted to obtain satisfactory simulations of the data. The major discrepancy observed was that the model tended to underpredict PAN by ca. 40% in the isoprene experiments, despite the fact that the model predicted PAN from methacrolein and MVK reasonably well. The uncertainties and additional data needed to completely characterize the isoprene atmospheric photooxidation system are discussed. © 1996 John Wiley & Sons, Inc.
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