Seasonal Aerosol Acidity, Liquid Water Content and Their Impact on Fine Urban Aerosol in SE Canada

Abstract

This study explores the drivers of aerosol pH and their impact on the inorganic fraction and mass of aerosol in the S.E. Canadian urban environments of Hamilton and Toronto, Ontario. We find that inter-seasonal pH variability is mostly driven by temperature changes, which cause variations of up to one pH unit. Wintertime acidity is reduced, compared to summertime values. Because of this, the response of aerosol to precursors fundamentally changes between seasons, with a strong sensitivity of aerosol mass to levels of HNO3 in the wintertime. Liquid water content (LWC) fundamentally influences the aerosol sensitivity to NH3 and HNO3 levels. In the summertime, organic aerosol is mostly responsible for the LWC at Toronto, and ammonium sulfate for Hamilton; in the winter, LWC was mostly associated with ammonium nitrate at both sites. The combination of pH and LWC in the two sites also affects N dry deposition flux; NO3− fluxes were comparable between the two sites, but NH3 deposition flux at Toronto is almost twice what was seen in Hamilton; from November to March N deposition flux slows down leading to an accumulation of N as NO3− in the particle phase and an increase in PM2.5 levels. Given the higher aerosol pH in Toronto, aerosol masses at this site are more sensitive to the emission of HNO3 precursors compared to Hamilton. For both sites, NOx emissions should be better regulated to improve air quality during winter; this is specifically important for the Toronto site as it is thermodynamically more sensitive to the emissions of HNO3 precursors.