Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

Abstract. Isoprene is a~precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO₂ levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry–climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work, we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the Master Chemical Mechanism) over a range of NO_x and isoprene emissions, through the use of O₃ isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NO_x reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene-rich regions, the response of the schemes varies considerably. The wide-ranging response is due to differences in the model descriptions of the peroxy radical chemistry, particularly their relative rates of reaction towards NO, leading to ozone formation, or HO₂, leading to termination. Also important is the yield of isoprene nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NO_x reservoir species, tend to produce more ozone locally and less away from the source region. We also note changes in other key oxidants such as NO₃ and OH (due to the inclusion of additional isoprene-derived HO_x recycling pathways). These have implications for secondary organic aerosol formation, as does the inclusion of an epoxide formation pathway in one of the mechanisms. By combining the emissions and O₃ data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements and laboratory studies are needed to validate these reduced mechanisms especially under high-volatile-organic-compound, low-NO_x conditions.