A comparison of chemical mechanisms using Tagged Ozone Production Potential (TOPP) analysis

Ground-level ozone is a secondary pollutant produced photochemically from reactions of NOx with peroxy radicals produced during volatile organic compound (VOC) degradation. Chemical transport models use simplified representations of this complex gas-phase chemistry to predict O3 levels and inform emission control strategies. Accurate representation of O3 production chemistry is vital for effective prediction. In this study, VOC degradation chemistry in simplified mechanisms is compared to that in the near-explicit Master Chemical Mechanism (MCM) using a box model and by "tagging" all organic degradation products over multi-day runs, thus calculating the tagged ozone production potential (TOPP) for a selection of VOCs representative of urban air masses. Simplified mechanisms that aggregate VOC degradation products instead of aggregating emitted VOCs produce comparable amounts of O3 from VOC degradation to the MCM. First-day TOPP values are similar across mechanisms for most VOCs, with larger discrepancies arising over the course of the model run. Aromatic and unsaturated aliphatic VOCs have the largest inter-mechanism differences on the first day, while alkanes show largest differences on the second day. Simplified mechanisms break VOCs down into smaller-sized degradation products on the first day faster than the MCM, impacting the total amount of O3 produced on subsequent days due to secondary chemistry.