Multiphase chemistry of NO ₂ and alkaline matter in aerosol water explains rapid sulfate formation and severe haze in China.

Extreme haze episodes repeatedly shrouded Beijing during the winter of 2012–2013, causing major environmental and health problems. To better understand these extreme events, we performed a model-assisted analysis of the hourly observation data of PM_2.5 and its major chemical compositions. The synthetic analysis shows that (1) the severe winter haze was driven by stable synoptic meteorological conditions over northeastern China, and not by an abrupt increase in anthropogenic emissions. (2) Secondary species, including organics, sulfate, nitrate, and ammonium, were the major constituents of PM_2.5 during this period. (3) Due to the dimming effect of high loading of aerosol particles, gaseous oxidant concentrations decreased significantly, suggesting a reduced production of secondary aerosols through gas-phase reactions. Surprisingly, the observational data reveals an enhanced production rate of secondary aerosols, suggesting an important contribution from other formation pathways, most likely heterogeneous reactions. These reactions appeared to be more efficient in producing secondary inorganics aerosols than organic aerosols resulting in a strongly elevated fraction of inorganics during heavily polluted periods. (4) Moreover, we found that high aerosol concentration was a regional phenomenon. The accumulation process of aerosol particles occurred successively from cities southeast of Beijing. The apparent sharp increase in PM_2.5 concentration of up to several hundred μg m⁻³ per hour recorded in Beijing represented rapid recovery from an interruption to the continuous pollution accumulation over the region, rather than purely local chemical production. This suggests that regional transport of pollutants played an important role during these severe pollution events.

Severe regional haze pollution events occurred in eastern and central China in January 2013, which had adverse effects on the environment and public health. Extremely high levels of particulate matter with aerodynamic diameter of 2.5 μm or less (PM_2.5) with dominant components of sulfate and nitrate are responsible for the haze pollution. Although heterogeneous chemistry is thought to play an important role in the production of sulfate and nitrate during haze episodes, few studies have comprehensively evaluated the effect of heterogeneous chemistry on haze formation in China by using the 3-D models due to of a lack of treatments for heterogeneous reactions in most climate and chemical transport models. In this work, the WRF-CMAQ model with newly added heterogeneous reactions is applied to East Asia to evaluate the impacts of heterogeneous chemistry and the meteorological anomaly during January 2013 on regional haze formation. As the parameterization of heterogeneous reactions on different types of particles is not well established yet, we arbitrarily selected the uptake coefficients from reactions on dust particles and then conducted several sensitivity runs to find the value that can best match observations. The revised CMAQ with heterogeneous chemistry not only captures the magnitude and temporal variation of sulfate and nitrate, but also reproduces the enhancement of relative contribution of sulfate and nitrate to PM_2.5 mass from clean days to polluted haze days. These results indicate the significant role of heterogeneous chemistry in regional haze formation and improve the understanding of the haze formation mechanisms during the January 2013 episode.

The clean air actions implemented by the Chinese government in 2013 have led to significantly improved air quality in Beijing. In this work, we combined the in situ measurements of the chemical components of submicron particles (PM₁) in Beijing during the winters of 2014 and 2017 and a regional chemical transport model to investigate the impact of clean air actions on aerosol chemistry and quantify the relative contributions of anthropogenic emissions, meteorological conditions, and regional transport to the changes in aerosol chemical composition from 2014 to 2017. We found that the average PM₁ concentration in winter in Beijing decreased by 49.5 % from 2014 to 2017 (from 66.2 to 33.4 µg m⁻³). Sulfate exhibited a much larger decline than nitrate and ammonium, which led to a rapid transition from sulfate-driven to nitrate-driven aerosol pollution during the wintertime. Organic aerosol (OA), especially coal combustion OA, and black carbon also showed large decreasing rates, indicating the effective emission control of coal combustion and biomass burning. The decreased sulfate contribution and increased nitrate fraction were highly consistent with the much faster emission reductions in sulfur dioxide (SO₂) due to phasing out coal in Beijing compared to reduction in nitrogen oxides emissions estimated by bottom-up inventory. The chemical transport model simulations with these emission estimates reproduced the relative changes in aerosol composition and suggested that the reduced emissions in Beijing and its surrounding regions played a dominant role. The variations in meteorological conditions and regional transport contributed much less to the changes in aerosol concentration and its chemical composition during 2014–2017 compared to the decreasing emissions. Finally, we speculated that changes in precursor emissions possibly altered the aerosol formation mechanisms based on ambient observations. The observed explosive growth of sulfate at a relative humidity (RH) greater than 50 % in 2014 was delayed to a higher RH of 70 % in 2017, which was likely caused by the suppressed sulfate formation through heterogeneous reactions due to the decrease in SO₂ emissions. Thermodynamic simulations showed that the decreased sulfate and nitrate concentrations have lowered the aerosol water content, particle acidity, and ammonium particle fraction. The results in this study demonstrate the response of aerosol chemistry to the stringent clean air actions and identify that the anthropogenic emission reductions are a major driver, which could help to further guide air pollution control strategies in China.

Water content and mass matter more than composition for the acidity of atmospheric aerosols in ammonia-buffered regions.