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

The Guadalquivir Valley is one of three major O hotspots in Spain. An airborne and surface measurement campaign was carried out from July 9th to 11th, 2019 to quantify the local/regional O 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 O and various tracer pollutants. O accumulation over 2.5 days started with inputs from oceanic air masses transported inland by sea breezes, which drew O 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 O concentration by 25-30 ppb. Furthermore, possible Mediterranean O contributions and additional vertical recirculation through the entrainment zone of the convective boundary layer also contributed. Using particulate matter finer than 2.5 μm (PM), ultrafine particles (UFP), and black carbon (BC) as tracers of local sources, we calculated that local contributions increased regional O 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 O. Meanwhile, a decreasing trend at high altitudes (3000-5000 m a.s.l.) was observed, signifying that the impact of stratospheric O intrusion decreased during the campaign.