Vertical profiles of isoprene and monoterpenes were measured by a proton transfer reaction-time of flight-mass spectrometry (PTR-ToF-MS) at heights of 3, 15, 32, 64, and 102 m above the ground on the Institute of Atmospheric Physics (IAP) tower in central Beijing during the winter of 2016 and the summer of 2017. Isoprene mixing ratios were larger in summer due to much stronger local emissions whereas monoterpenes were lower in summer due largely to their consumption by much higher levels of ozone. Isoprene mixing ratios were the highest at the 32 m in summer (1.64 ± 0.66 ppbV) and at 15 m in winter (1.41 ± 0.64 ppbV) with decreasing concentrations to the ground and to the 102 m, indicating emission from the tree canopy of the surrounding parks. Monoterpene mixing ratios were the highest at the 3 m height in both the winter (0.71 ± 0.42 ppbV) and summer (0.16 ± 0.10 ppbV) with a gradual decreasing trend to 102 m, indicting an emission from near the ground level. The lowest isoprene and monoterpene mixing ratios all occurred at 102 m, which were 0.71 ± 0.42 ppbV (winter) and 1.35 ± 0.51 ppbV (summer) for isoprene, and 0.42 ± 0.22 ppbV (winter) and 0.07 ± 0.06 ppbV (summer) for monoterpenes. Isoprene in the summer and monoterpenes in the winter, as observed at the five heights, showed significant mutual correlations. In the winter monoterpenes were positively correlated with combustion tracers CO and acetonitrile at 3 m, suggesting possible anthropogenic sources.

Abstract. Intermediate-volatility organic compounds (IVOCs) emitted from vehicles are important precursors to secondary organic aerosols (SOAs) in urban areas, yet vehicular emission of IVOCs, particularly from on-road fleets, is poorly understood. Here we initiated a field campaign to collect IVOCs with sorption tubes at both the inlet and the outlet in a busy urban tunnel (>30 000 vehicles per day) in south China for characterizing emissions of IVOCs from on-road vehicles. The average emission factor of IVOCs (EFIVOCs) was measured to be 16.77±0.89 mg km−1 (average ±95 % CI, confidence interval) for diesel and gasoline vehicles in the fleets, and based on linear regression, the average EFIVOCs was derived to be 62.79±18.37 mg km−1 for diesel vehicles and 13.95±1.13 mg km−1 for gasoline vehicles. The EFIVOCs for diesel vehicles from this study was comparable to that reported previously for non-road engines without after-treatment facilities, while the EFIVOCs for gasoline vehicles from this study was much higher than that recently tested for a China V gasoline vehicle. IVOCs from the on-road fleets did not show significant correlation with the primary organic aerosol (POA) or total non-methane hydrocarbons (NMHCs) as results from previous chassis dynamometer tests. Estimated SOA production from the vehicular IVOCs and VOCs surpassed the POA by a factor of ∼2.4, and IVOCs dominated over VOCs in estimated SOA production by a factor of ∼7, suggesting that controlling IVOCs is of greater importance to modulate traffic-related organic aerosol (OA) in urban areas. The results demonstrated that although on-road gasoline vehicles have much lower EFIVOCs, they contribute more IVOCs than on-road diesel vehicles due to its dominance in the on-road fleets. However, due to greater diesel than gasoline fuel consumption in China, emission of IVOCs from diesel engines would be much larger than that from gasoline engines, signaling the overwhelming contribution of IVOC emissions by non-road diesel engines in China.