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Abstract

Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM2.5 sulfate (Δ17O(SO42−)) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM2.5 concentrations ranged from 16 to 323µg m−3 with a mean of (141  ±  88 (1σ))µg m−3, with SO42− representing 8–25% of PM2.5 mass. The observed Δ17O(SO42−) varied from 0.1 to 1.6‰ with a mean of (0.9  ±  0.3)‰. Δ17O(SO42−) increased with PM2.5 levels in October 2014 while the opposite trend was observed from November 2014 to January 2015. Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM2.5  ≥  75µg m−3) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68%. During PDs of Cases I and III–V, heterogeneous sulfate production (Phet) was estimated to contribute 41–54% to total sulfate formation with a mean of (48  ±  5)%. For the specific mechanisms of heterogeneous oxidation of SO2, chemical reaction kinetics calculations suggested S(IV) ( = SO2 ⚫H2O+HSO3−  +  SO32−) oxidation by H2O2 in aerosol water accounted for 5–13% of Phet. The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed Δ17O(SO42−). Heterogeneous sulfate production via S(IV) oxidation by O3 was estimated to contribute 21–22% of Phet on average. Heterogeneous sulfate production pathways that result in zero-Δ17O(SO42−), such as S(IV) oxidation by NO2 in aerosol water and/or by O2 via a radical chain mechanism, contributed the remaining 66–73% of Phet. The assumption about the thermodynamic state of aerosols (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6  ±  0.1 or 4.7  ±  1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO2 and by O2. Our local atmospheric conditions-based calculations suggest sulfate formation via NO2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of Δ17O(SO42−) for quantifying sulfate formation pathways, but this estimate may be further improved with future regional modeling work.