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We investigated the spatial-temporal characteristics of the correlations between observed PM2.5 and O3 over China at a national-scale level, and examined the underlying reasons for the varying PM2.5–O3 correlations by using a chemical transport model. The PM2.5 concentrations were positively correlated with O3 concentrations for most regions and seasons over China, while negative correlations were mainly observed in northern China during winter. The strongest positive PM2.5–O3 correlations with correlation coefficients (r) larger than +0.7 existed in southern China during July, and the strongest negative correlations (r < −0.5) were observed in northern China during January. It was a very interesting phenomenon that the positive PM2.5–O3 correlations prevailed for high air temperature samples, while the negative correlations were generally found in cold environments. Together, the effective inhibitory effect of PM2.5 on O3 generation by reducing photolysis rates and the strong titration effect of freshly emitted NO with O3 contributed to the strongest negative PM2.5–O3 correlations in northern China during January (i.e., in cold environments). The strongest positive correlations in southern China during July (i.e., at high temperature), however, were mainly attributed to the promoting effect of high O3 concentration and active photochemical activity on secondary particle formation.

Correlations between PM2.5 and Ozone over China and Associated Underlying Reasons