Variability of atmospheric ammonia related to potential emission sources in downtown Toronto, Canada

The variability of atmospheric ammonia (NH3) in downtown Toronto was investigated through the analysis of 24 hr integrated denuder NH3 samples collected at a site above a street canyon every third day from July 2003 to September 2011 (Dataset 1). The measured NH3 mixing ratios ranged from below the detection limit to 14.7 ppb during the eight-year period. Distinctive seasonal variations were observed with summer averages (+/- standard deviation) of 3.9 +/- 1.6 ppb and winter averages of 1.1 +/- 0.6 ppb. Two other datasets, weekly/biweekly passive samples of NH3 monitored at 74 agricultural and remote sites across southern Ontario during the period of June 2006 to March 2007 (Dataset 2) and semi-continuous measurements of NH3 and ammonium (pNH(4)(+)) in PM2.5 collected at a site inside a street canyon approximately 170 m away from the downtown site in December 2008 and February, March and May 2009 (Dataset 3), were further used to evaluate the potential NH3 sources in downtown Toronto. The NH3 mixing ratios at the downtown location were higher than those at the surrounding agricultural sites, and the mixing ratios within the street canyon were almost double those measured above it. These results suggested that the observed NH3 at the downtown location was mainly from local sources within the street canyon. Analysis of Dataset 3 showed that the diurnal cycles of NH3 at the downtown location cannot be simply explained by traffic and water consumption patterns. A green space inside the street canyon was identified as a potential important source contributing to the observed NH3 when T > 0 degrees C. However, the major NH3 emission sources at T <= 0 degrees C are yet to be investigated. (C) 2014 Elsevier Ltd. All rights reserved.