High gaseous carbonyl concentrations in the upper boundary layer in Shijiazhuang, China.

Oxygenated volatile organic compounds (OVOCs) are important precursors of secondary air pollutants. However, knowledge of the vertical characteristics of OVOCs in the lower troposphere is lacking. Pairs of OVOCs samples were simultaneously collected via 2,4-dinitrophenylhydrazine (DNPH) near the ground and in the upper boundary layer (at 500 m in winter and 600 m in summer) with a tethered balloon in Shijiazhuang in January and June 2019. The samples were analyzed via high-performance liquid chromatography (HPLC), and 26 vertical profiles of 13 OVOCs were obtained in this study. In winter, the average concentrations of the total OVOCs (TOVOCs) in the upper boundary layer and near the ground were 7.9 ± 4.1 ppbv and 5.5 ± 2.8 ppbv, respectively; while in summer, the average concentrations were 7.1 ± 3.5 ppbv and 6.5 ± 2.7 ppbv, respectively. Acetone, formaldehyde and acetaldehyde were the three main components accounting for more than 80% of the TOVOCs. Significant vertical differences were observed before sunrise in winter and in the afternoon in summer. The TOVOCs concentration in the residual layer (8.4 ± 3.6 ppbv) was higher than that near the ground (6.0 ± 2.5 ppbv), while in the summer afternoon, the concentration in the upper mixing layer (ML) (9.5 ± 2.2 ppbv) was higher than that near the ground (5.8 ± 3.1 ppbv). OVOCs sources were examined with a positive matrix factorization (PMF) model. In winter, the small-molecule carbonyls (SMCs) in the upper boundary layer are mainly derived from secondary + long-lived species (68.4%) because volatile organic compounds at high concentrations were oxidized into OVOCs. In summer, the SMCs in the upper ML were mainly affected by elevated industrial point source emissions (42.9%). These data indicate that vertical gradient observations of SMCs are an important supplement to advance current air pollution research.