Seasonal behavior of PM2.5 deliquescence, crystallization, and hygroscopic growth in the Po Valley (Milan): Implications for remote sensing applications

Abstract

Atmospheric aerosols deliquescence and crystallization relative humidity (DRH and CRH) are rarely measured compared to the worldwide number of hygroscopicity measurements; this feature comes from the lack of an efficient method able to capture the whole complexity of chemical composition of aerosols. Despite this, the knowledge of both DRH and CRH are crucial for a correct parameterization of the aerosol hygroscopic growth used in different applications, among which the remote sensing is very important.In this paper, a newly developed technique (direct current conductance method) was applied in an aerosol chamber to Milan PM2.5 samples, to identify aerosol DRH and CRH both during winter and summer. These results were compared with those independently obtained by gravimetric measurements conducted in the chamber using a microbalance. Microbalance data allowed also the determination of the mass hygroscopic growth factor on the collected PM2.5 samples.Results evidenced first a good agreement between the two methods (RMSE=2.7% and 2.3% for DRH and CRH, respectively). Collected data evidenced the hysteresis behavior of ambient particles and variability in both DRH and CRH between the two seasons. Summer samples showed higher DRH and CRH (on average 71.4±1.0% RH and 62.6±1.2% RH, respectively) than the winter ones (on average 55.2±0.7% RH and 46.9±0.6% RH). This behavior was related to the higher content of sulfates during the summer season. Conversely, the mass hygroscopic growth factor at 90% RH was higher for winter samples (2.76±0.06) with respect to the summer ones (1.91±0.11).Since hysteresis behavior affects optical properties of aerosols, when RH conditions are within the loop, the hygroscopic growth factor could be assigned in a wrong way. Thus, the growth factor was calculated within the hysteresis loop for both upper and lower branches: results showed that difference in hygroscopic growth factor could reach up the 24%.