Understanding the local and remote source contributions to ambient O3 during a pollution episode using a combination of experimental approaches in the Guadalquivir valley, southern Spain

The Guadalquivir Valley is one of three major O3 hotspots in Spain. An airborne and surface measurement campaign was carried out from July 9th to 11th, 2019 to quantify the local/regional O3 contributions using experimental approaches. Air quality and meteorology data from surface measurements, a microlight aircraft, a helium balloon, and remote sensing data (TROPOMI-NO2-ESA) were used to obtain the 3D distribution of O3 and various tracer pollutants. O3 accumulation over 2.5 days started with inputs from oceanic air masses transported inland by sea breezes, which drew O3 and its precursors from a local/regional origin to the northeastern end of the basin. The orographic–meteorological setting of the valley caused vertical recirculation of the air masses inside the valley that caused the accumulation by increasing regional background O3 concentration by 25–30 ppb. Furthermore, possible Mediterranean O3 contributions and additional vertical recirculation through the entrainment zone of the convective boundary layer also contributed. Using particulate matter finer than 2.5 µm (PM2.5), ultrafine particles (UFP), and black carbon (BC) as tracers of local sources, we calculated that local contributions increased regional O3 levels by 20 ppb inside specific pollution plumes transported by the breeze into the valley, and by 10 ppb during midday when flying over an area with abundant agricultural burning during the morning. Air masses that crossed the southern boundaries of the Betic system at mid-altitude (400–1850 m a.s.l.) on July 10th and 11th may have provided additional O3. Meanwhile, a decreasing trend at high altitudes (3000–5000 m a.s.l.) was observed, signifying that the impact of stratospheric O3 intrusion decreased during the campaign.The present work was supported by the Spanish Ministry for Ecological Transition (17CAES010); the “Agencia Estatal de Investigación” from the Spanish Ministry of Science, Innovation and Universities and FEDER funds under the project HOUSE (CGL2016-78594-R); the Agencia Estatal de Investigación (RTI2018-095937-B-I00); and the Generalitat de Catalunya (AGAUR 2017 SGR41). We would like to thank the Junta de Andalucía for providing us with air quality data, and the Spanish Met Office (AEMET) for providing meteorological data and facilitating staff and instrumentation for the soundings, as well as ESA for providing TROPOMI-NO2 data and NOAA for the HYSPLIT modeling tool. Cristina Carnerero thanks “Agencia Estatal de Investigación” for the grant received to carry out her PhD (FPI grant: BES-2017-080027). Carlos Pérez García-Pando acknowledges support by the AXA Research Fund, and the Spanish Ministry of Science, Innovation and Universities (RYC-2015-18690).Peer ReviewedPostprint (published version