Urban Single Precipitation Events: A Key for Characterizing Sources of Air Contaminants and the Dynamics of Atmospheric Chemistry Exchanges

The chemistry of atmospheric precipitation serves as an important proxy for discriminating the source(s) of air contaminants in urban environments as well as to discuss the dynamic of atmospheric chemistry exchanges. This approach can be undertaken at time scales varying from single events to seasonal and yearly time frames. Here, we characterized the chemical composition of two single rain episodes (18 July 2018 and 21 February 2019) collected in Wrocław (SW Poland). Our results demonstrated inner variations and seasonality (within the rain event as well as between summer and winter), both in ion concentrations as well as in their potential relations with local air contaminants and scavenging processes. Coupling statistical analysis of chemical parameters with meteorological/synoptic conditions and HYSPLIT back trajectories allowed us to identify three main factors (i.e., principal components; PC) controlling the chemical composition of precipitation, and that these fluctuated during each event: (i) PC1 (40%) was interpreted as reflecting the long-range transport and/or anthropogenic influences of emission sources that included biomass burning, fossil fuel combustion, industrial processes, and inputs of crustal origin; (ii) PC2 (20%) represents the dissolution of atmospheric CO2 and HF into ionic forms; and (iii) PC3 (20%) originates from agricultural activities and/or biomass burning. Time variations during the rain events showed that each factor was more important at the start of the event. The study of both SO42− and Ca2+ concentrations showed that while sea spray inputs fluctuated during both rain events, their overall impact was relatively low. Finally, below-cloud particle scavenging processes were only observed for PM10 at the start of the winter rain episode, which was probably explained by the corresponding low rain intensity and an overlap from local aerosol emissions. Our study demonstrates the importance of multi-time scale approaches to explain the chemical variability in rainwater and both its relation to emission sources and the atmosphere operating processes.