Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO 2 by NO 2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH 3 neutralization or under cloud conditions. Under polluted environments, this SO 2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH 3 and NO 2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.sulfate aerosol | severe haze | pollution | human health | climate

Abstract. The chemical mechanisms responsible for rapid sulfate production, an important driver of winter haze formation in northern China, remain unclear. Here, we propose a potentially important heterogeneous hydroxymethanesulfonate (HMS) chemical mechanism. Through analyzing field measurements with aerosol mass spectrometry, we show evidence for a possible significant existence in haze aerosols of organosulfur primarily as HMS, misidentified as sulfate in previous observations. We estimate that HMS can account for up to about one-third of the sulfate concentrations unexplained by current air quality models. Heterogeneous production of HMS by SO2 and formaldehyde is favored under northern China winter haze conditions due to high aerosol water content, moderately acidic pH values, high gaseous precursor levels, and low temperature. These analyses identify an unappreciated importance of formaldehyde in secondary aerosol formation and call for more research on sources and on the chemistry of formaldehyde in northern China winter.

Size-resolved airborne particles (9-stages) in urban Xi'an, China, during summer and winter were measured for molecular distributions and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls. To our best knowledge, we report for the first time the size-resolved differences in stable carbon isotopic compositions of diacids and related compounds in continental organic aerosols. High ambient concentrations of terephthalic (tPh, 379 ± 200 ng m(-3)) and glyoxylic acids (ωC(2), 235 ± 134 ng m(-3)) in Xi'an aerosols during winter compared to those in other Chinese cities suggest significant emissions from plastic waste burning and coal combustions. Most of the target compounds are enriched in the fine mode (<2.1 μm) in both seasons peaking at 0.7-2.1 μm. However, summertime concentrations of malonic (C(3)), succinic (C(4)), azelaic (C(9)), phthalic (Ph), pyruvic (Pyr), 4-oxobutanoic (ωC(4)), and 9-oxononanoic (ωC(9)) acids, and glyoxal (Gly) in the coarse mode (>2.1 μm) are comparable to and even higher than those in the fine mode (<2.1 μm). Stable carbon isotopic compositions of the major organics are higher in winter than in summer, except oxalic acid (C(2)), ωC(4), and Ph. δ(13)C of C(2) showed a clear difference in sizes during summer, with higher values in fine mode (ranging from -22.8‰ to -21.9‰) and lower values in coarse mode (-27.1‰ to -23.6‰). The lower δ(13)C of C(2) in coarse particles indicate that coarse mode of the compound originates from evaporation from fine mode and subsequent condensation/adsorption onto pre-existing coarse particles. Positive linear correlations of C(2), sulfate and ωC(2) and their δ(13)C values suggest that ωC(2) is a key intermediate, which is formed in aqueous-phase via photooxidation of precursors (e.g., Gly and Pyr), followed by a further oxidation to produce C(2).