Abstract. A mobile laboratory equipped with state-of-the-art gaseous and particulate instrumentation was deployed across the Greater Toronto Area during two seasons. A high-resolution time-of-flight mass spectrometer (HR-TOF-CIMS) measured isocyanic acid (HNCO) and hydrogen cyanide (HCN), and a high-sensitivity laser-induced incandescence (HS-LII) instrument measured black carbon (BC). Results indicate that on-road vehicles are a clear source of HNCO and HCN, and that their impact is more pronounced in the winter, when influences from biomass burning and secondary photochemistry are weakest. Plume-based and time-based algorithms were developed to calculate fleet-average vehicle emission factors (EF); the algorithms were found to yield comparable results, depending on the pollutant identity. With respect to literature EFs for benzene, toluene, C2 benzene (sum of m,p,o-xylenes and ethylbenzene), nitrogen oxides, particle number concentration (PN), and black carbon, the calculated EFs were characteristic of a relatively clean vehicle fleet dominated by light-duty vehicles. Our fleet-average EF for BC (median: 25 mg kgfuel−1, interquartile range: 10–76 mg kgfuel−1) suggests that overall vehicular emissions of BC have decreased over time. However, the distribution of EFs indicates that a small proportion of high-emitters continue to contribute disproportionately to total BC emissions. We report the first fleet-average EF for HNCO (median: 2.3 mg kgfuel−1, interquartile range: 1.4–4.2 mg kgfuel−1) and HCN (median: 0.52 mg kgfuel−1, interquartile range: 0.32–0.88 mg kgfuel−1). The distribution of the estimated EFs provides insight into the real-world variability of HNCO and HCN emissions, and constrains the wide range of literature EFs obtained from prior dynamometer studies. Our results demonstrate that although biomass burning is a dominant source of both air toxics on a national scale, vehicular emissions play an increasingly important role at a local scale, especially in heavily-trafficked urban areas. The impact of vehicle emissions on urban HNCO levels can be expected to be further enhanced if secondary HNCO formation from vehicle exhaust is considered.
Aerosol particle mixing state, refractory particle number size distributions and emission factors in a polluted urban environment: Case study of Metro Manila, Philippines
