Environmental Chamber Studies of Atmospheric Reactivities of Volatile Organic Compounds: Effects of Varying Chamber and Light Source

Photochemical oxidant models are essential tools for assessing effects of emissions changes on ground-level ozone formation. Such models are needed for predicting the ozone impacts of increased alternative fuel use. The gas-phase photochemical mechanism is an important component of these models because ozone is not emitted directly, but is formed from the gas-phase photochemical reactions of the emitted volatile organic compounds (VOCs) and oxides of nitrogen (NO{sub x}) in air. The chemistry of ground level ozone formation is complex; hundreds of types of VOCs being emitted into the atmosphere, and most of their atmospheric reactions are not completely understood. Because of this, no chemical model can be relied upon to give even approximately accurate predictions unless it has been evaluated by comparing its predictions with experimental data. Therefore an experimental and modeling study was conducted to assess how chemical mechanism evaluations using environmental chamber data are affected by the light source and other chamber characteristics. Xenon arc lights appear to give the best artificial representation of sunlight currently available, and experiments were conducted in a new Teflon chamber constructed using such a light source. Experiments were also conducted in an outdoor Teflon Chamber using new procedures to improve the light characterization, and in Teflon chambers using blacklights. These results, and results of previous runs other chambers, were compared with model predictions using an updated detailed chemical mechanism. The magnitude of the chamber radical source assumed when modeling the previous runs were found to be too high; this has implications in previous mechanism evaluations. Temperature dependencies of chamber effects can explain temperature dependencies in chamber experiments when Ta-300{degree}K, but not at temperatures below that.