Large petrochemical complex (PC) widely exists in both developing and developed countries, and is expected to have a special photochemical pollution in local scale due to huge VOCs emissions. Here, a typical large-scale PC in North China was selected as the study case, to explore the character, formation and influence of local photochemical pollution regarding PCs based on an improved 0-D chemical model. In the study PC, VOCs-rich character was apparent with THCs level of 90.8 ± 28.0 ppb and THCs/NOx ratio of ∼26.2 mol/mol. Severe O3 pollution was found in warm months with monthly mean MDA1O3 of 67.3–96.0 ppb. Model simulations showed the heavy O3 pollution in this PC was attributed to high precursors rather than to unfavorable meteorology, and was more sensitive to NOx (with response of 1.42 g/g) than to THCs (with response of 0.12 g/g). The photochemical pollution formation potential of the emission plumes of this PC was very enormous, with production rate of 19.6 ppb h−1 for O3, 2.9 ppb h−1 for HCHO and 1.1 ppb h−1 for CH3CHO on daytime average, 1–5 greater than in normal urban areas. The higher production rates happened in morning hours, which explained the earlier peak time of observed O3 in PCs. And about 70% of photochemical pollution (represented by O3) would be transported to surroundings, leading to the significant photochemical-pollution hazard to the vicinity of PCs.
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