First long-term surface ozone variations at an agricultural site in the North China Plain: Evolution under changing...

Significant upward trends in surface ozone (O₃) have been widely reported in China during recent years, especially during warm seasons in the North China Plain (NCP), exerting adverse environmental effects on human health and agriculture. Quantifying long-term O₃ variations and their attributions helps to understand the causes of regional O₃ pollution and to formulate according control strategy. In this study, we present long-term trends of O₃ in the warm seasons (April-September) during 2006-2019 at an agricultural site in the NCP and investigate the relative contributions of meteorological and anthropogenic factors. Overall, the maximum daily 8-h average (MDA8) O₃ exhibited a weak decreasing trend with large interannual variability. < 6 % of the observed trend could be explained by changes in meteorological conditions, while the remaining 94 % was attributed to anthropogenic impacts. However, the interannual variability of warm season MDA8 O₃ was driven by both meteorology (36 ± 28 %) and anthropogenic factors (64 ± 27 %). Daily maximum temperature was the most essential factor affecting O₃ variations, followed by ultraviolet radiation b (UVB) and boundary layer height (BLH), with rising temperature trends inducing O₃ inclines throughout April to August, while UVB mainly influenced O₃ during summer months. Under changes in emissions and air quality, warm season O₃ production regime gradually shifted from dominantly VOCs-limited during 2006-2015 to NO_x-limited afterwards. Relatively steady HCHO and remarkably rising NO_x levels resulted in the fast decreasing MDA8 O₃ (-2.87 ppb yr^-1) during 2006-2012. Rapidly decreasing NO_x, flat or slightly increasing HCHO promoted O₃ increases during 2012-2015 (9.76 ppb yr^-1). While afterwards, slow increases in HCHO and downwards fluctuating NO_x led to decreases in MDA8 O₃ (-4.97 ppb yr^-1). Additionally, continuous warming trends might promote natural emissions of O₃ precursors and magnify their impacts on agricultural O₃ by inducing high variability, which would require even more anthropogenic reduction to compensate for.