Ozone source apportionment during peak summer events over southwestern Europe

It is well established that in Europe, high O₃ concentrations are most pronounced in southern/Mediterranean countries due to the more favourable climatological conditions for its formation. However, the contribution of the different sources of precursors to O₃ formation within each country relative to the imported (regional and hemispheric) O₃ is poorly quantified. This lack of quantitative knowledge prevents local authorities from effectively designing plans that reduce the exceedances of the O₃ target value set by the European air quality directive. O₃ source attribution is a challenge because the concentration at each location and time results not only from local biogenic and anthropogenic precursors, but also from the transport of O₃ and precursors from neighbouring regions, O₃ regional and hemispheric transport and stratospheric O₃ injections. The main goal of this study is to provide a first quantitative estimation of the contribution of the main anthropogenic activity sectors to peak O₃ events in Spain relative to the contribution of imported (regional and hemispheric) O₃. We also assess the potential of our source apportionment method to improve O₃ modelling. Our study applies and thoroughly evaluates a countrywide O₃ source apportionment method implemented in the CALIOPE air quality forecast system for Spain at high resolution (4 × 4 km²) over a 10-day period characterized by typical summer conditions in the Iberian Peninsula (IP). The method tags both O₃ and its gas precursor emissions from source sectors within one simulation, and each tagged species is subject to the typical physico-chemical processes (advection, vertical mixing, deposition, emission and chemistry) as the actual conditions remain unperturbed. We quantify the individual contributions of the largest NO _x local sources to high O₃ concentrations compared with the contribution of imported O₃. We show, for the first time, that imported O₃ is the largest input to the ground-level O₃ concentration in the IP, accounting for 46 %-68 % of the daily mean O₃ concentration during exceedances of the European target value. The hourly imported O₃ increases during typical northwestern advections (70 %-90 %, 60-80 microg m^-3), and decreases during typical stagnant conditions (30 %-40 %, 30-60 microg m^-3) due to the local NO titration. During stagnant conditions, the local anthropogenic precursors control the O₃ peaks in areas downwind of the main urban and industrial regions (up to 40 % in hourly peaks). We also show that ground-level O₃ concentrations are strongly affected by vertical mixing of O₃-rich layers present in the free troposphere, which result from local/regional layering and accumulation, and continental/hemispheric transport. Indeed, vertical mixing largely explains the presence of imported O₃ at ground level in the IP. Our results demonstrate the need for detailed quantification of the local and remote contributions to high O₃ concentrations for local O₃ management, and show O₃ source apportionment to be an essential analysis prior to the design of O₃ mitigation plans in any non-attainment area. Achieving the European O₃ objectives in southern Europe requires not only ad hoc local actions but also decided national and European-wide strategies.