Integrating ambient carbonyl compounds provides insight into the constrained ozone formation chemistry in Zibo city of the North China Plain

Abstract

Quantifying the impact of carbonyl compounds (carbonyls) on ozone (O3) photochemical formation is crucial to formulating targeted O3 mitigation strategies. To investigate the emission source of ambient carbonyls and their integrated observational constraint on the impact of O3 formation chemistry, a field campaign was conducted in an industrial city (Zibo) of the North China Plain from August to September 2020. The site-to-site variations of OH reactivity for carbonyls were in accordance with the sequence of Beijiao (BJ, urban, 4.4 s−1) > Xindian (XD, suburban, 4.2 s−1) > Tianzhen (TZ, suburban, 1.6 s−1). A 0-D box model (MCMv3.3.1) was applied to assess the O3-precursor relationship influenced by measured carbonyls. It was found that without carbonyls constraint, the O3 photochemical production of the three sites was underestimated to varying degrees, and the biases of overestimating the VOC-limited degree were also identified through a sensitivity test to NOx emission changes, which may be associated with the reactivity of carbonyls. In addition, the results of the positive matrix factorization (PMF) model indicated that the main source of aldehydes and ketones was secondary formation and background (81.6% for aldehydes, 76.8% for ketones), followed by traffic emission (11.0% for aldehydes, 14.0% for ketones). Incorporated with the box model, we found that biogenic emission contributed the most to the O3 production at the three sites, followed by traffic emission as well as industry and solvent usage. Meanwhile, the relative incremental reactivity (RIR) values of O3 precursor groups from diverse VOC emission sources featured consistencies and differences at the three sites, which further highlights the importance of the synergetic mitigation of target O3 precursors at regional and local scales. This study will help to provide targeted policy-guiding O3 control strategies for other regions.