PM 2.5 during severe winter haze in Beijing, China, has reached levels as high as 880μg/m3, with sulfur compounds contributing significantly to PM 2.5 composition. This sulfur has been traditionally assumed to be sulfate, although atmospheric chemistry models are unable to account for such large sulfate enhancements under dim winter conditions. Using a 1-D model, we show that well-characterized but previously overlooked chemistry of aqueous-phase HCHO and S(IV) in cloud droplets to form a S(IV)-HCHO adduct, hydroxymethane sulfonate, may explain high particulate sulfur in wintertime Beijing. We also demonstrate in the laboratory that methods of ion chromatography typically used to measure ambient particulates easily misinterpret hydroxymethane sulfonate as sulfate. Our findings suggest that HCHO and not SO2 has been the limiting factor in many haze events in Beijing and that to reduce severe winter pollution in this region, policymakers may need to address HCHO sources such as transportation.
This study examines the sensitivity of “top-down” quantification of Chinese black carbon (BC) emissions to the temporal resolution of surface observations and to the transport model error associated with the grid resolution and wet deposition. At two rural sites (Miyun in North China Plain and Chongming in Yangtze River Delta), the model-inferred emission bias based on hourly BC observations can differ by up to 41% from that based on monthly mean observations. This difference relates to the intrinsic inability of the grid-based model in simulating high pollution plumes, which often exert a larger influence on the arithmetic mean of observations at monthly time steps. Adopting the variation of BC to carbon monoxide correlation slope with precipitation as a suitable measure to evaluate the model's wet deposition, we found that wet removal of BC in the model was too weak, due in part to the model's underestimation of large precipitation events. After filtering out the observations during high pollution plumes and large precipitation events for which the transport model error should not be translated into the emission error, the inferred emission bias changed from −11% (without filtering) to −2% (with filtering) at the Miyun site, and from −22% to +1% at the Chongming site. Using surface BC observations from three more rural sites (located in Northeast, Central, and Central South China, respectively) as constraints, our top-down estimate of total BC emissions over China was 1.80 ± 0.65 Tg/yr in 2006, 0.5% lower than the bottom-up inventory of Zhang et al. (2009) but with smaller uncertainty.