The impact of reducing industrial emissions of volatile organic compounds (VOCs) on ozone (O3) pollution is of wide concern particularly in highly industrialized megacities. In this study, O3, nitrogen oxides (NOx) and VOCs were measured at an urban site in the Pearl River Delta region during the 2018 Chinese National Day Holidays and two after-holiday periods (one with ozone pollution and another without). O3 pollution occurred throughout the 7-day holidays even industrial emissions of VOCs were passively reduced due to temporary factory shutdowns, and the toluene to benzene ratios dropped from ∼10 during non-holidays to ∼5 during the holidays. Box model (AtChem2-MCM) simulations with the input of observation data revealed that O3 formation was all VOC-limited, and alkenes had the highest relative incremental reactivity (RIR) during the holiday and non-holiday O3 episodes while aromatics had the highest RIR during the non-pollution period. Box model also demonstrated that even aromatics decreased proportionally to levels with near-zero contributions of industrial aromatic solvents, O3 concentrations would only decrease by less than 20% during the holiday and non-holiday O3 episodes and ozone pollution in the periods could not be eliminated. The results imply that controlling emissions of industrial aromatic solvents might be not enough to eliminate O3 pollution in the region, and more attention should be paid to anthropogenic reactive alkenes. Isoprene and formaldehyde were among the top 3 species by RIRs in all the three pollution and non-pollution periods, suggesting substantial contribution to O3 formation from biogenic VOCs.
Keywords: Box model; Master Chemical Mechanism (MCM); Ozone; Ozone precursors; Volatile organic compounds.
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