Relating high ozone, ultrafine particles, and new particle formation episodes using cluster analysis

Abstract

We studied the simultaneity of tropospheric ozone (O3) episodes, high ultrafine particle (UFP; diameter < 100 nm) concentrations, and the occurrence of new particle formation at a regional background station in the Western Mediterranean (northeast Spain), which is affected considerably by the transport of pollutants emitted in the Barcelona metropolitan area and nearby populated and industrial areas. Using cluster analysis, we categorized summer and spring days between 2014 and 2018 according to their daily cycles of O3 concentrations, and then studied the evolution of the particle number size distribution, meteorological variables, and black carbon and sulfur dioxide concentrations. The analysis revealed that, in spring and summer, the highest UFP concentrations coincided with the highest O3 episodes, but new particle formation was largely inhibited during these episodes, probably due to the high aerosol pollution load transported from the Barcelona metropolitan area to the station. In contrast, new particle formation episodes were concurrent with the lowest concentrations of O3 and UFPs, including the number of particles in the 9–25 nm size range. Measurements carried out in an intensive field study, using an air ion spectrometer and a particle size magnifier, support these results. In addition, measurements obtained onboard tethered balloons revealed that sea and land breezes transported regional pollutants vertically up to about 400 m above ground level. This coincided with episodes of vertical recirculation of air masses that lasted for several days, which resulted in high O3 and high UFP episodes, while new particle formation was inhibited. Keywords: Tropospheric ozone, Ultrafine particles, Photochemical pollutants, Cluster analysis, Rural station, Urban influence, Balloon soundings, Vertical distribution