An aerosol time-of-flight mass spectrometer (ATOFMS) was used to detect trimethylamine (TMA) in 0.52-1.9 μm particles at urban and rural sites in Southern Ontario during the summer and winter of 2007. During the summer, TMA-containing particles were observed exclusively during high relative humidity or fog events at both the urban and rural sites. In the wintertime, greater concentrations of TMA-containing particles were linked to cloud processing of aerosol in air masses originating from over agricultural and livestock areas. A laboratory study revealed that, at high relative humidity (∼ 100%), gas phase TMA at concentrations ranging from 2 to 20,000 ppt partitions preferentially to acidic particles present in the ambient air. On the basis of the field and laboratory studies, it appears that gas phase TMA present in ambient air partitions onto pre-existing particles preferentially during periods of acidic cloud/fog processing, leading to the presence of TMA-containing particles in the 0.52-1.9 μm size range.