A 10-day winter sampling campaign was conducted in downtown Toronto for particulate matter (PM) air pollution in the fine (<2.5 microm) size range. An aerosol laser ablation mass spectrometer (LAMS), a tapered-element oscillating microbalance (TEOM), and an aerodynamic particle sizer (APS) were operated in parallel to characterize the PM on-line. In this study, the LAMS observed differences in the chemical composition between three separate episodes with higher PM2.5 mass and APS counts. LAMS results showed that in one instance of elevated PM, organic amines were present in the particulates. Temporal analyses of this episode revealed chemical transformations as the amines, characterized by m/z peaks 58(C3HeN)+, 86(C5H2N)+, and nitrates, increased in number concentration while Ca and hydrocarbon particle classes concurrently decreased. On another day, sulfates were found to have increased significantly. The third event was only 4 h in duration and exhibited an increase in the number of submicron-sized K/hydrocarbons and sulfate-containing particles. In this last event, the hydrocarbons and a K to Fe ratio enrichment indicated there was likely a contribution from a combustion source. This work offers some of the first insights into single particle size and chemistry in a cold winter climate.