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 SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 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 NH3 and NO2 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.

https://www.pnas.org/content/pnas/113/48/13630.full.pdf

Persistent sulfate formation from London Fog to Chinese haze

Regional severe haze represents an enormous environmental problem in China, influencing air quality, human health, ecosystem, weather, and climate. These extremes are characterized by exceedingly high concentrations of fine particulate matter (smaller than 2.5 µm, or PM2.5) and occur with extensive temporal (on a daily, weekly, to monthly timescale) and spatial (over a million square kilometers) coverage. Although significant advances have been made in field measurements, model simulations, and laboratory experiments for fine PM over recent years, the causes for severe haze formation have not yet to be systematically/comprehensively evaluated. This review provides a synthetic synopsis of recent advances in understanding the fundamental mechanisms of severe haze formation in northern China, focusing on emission sources, chemical formation and transformation, and meteorological and climatic conditions. In particular, we highlight the synergetic effects from the interactions between anthropogenic emissions and atmospheric processes. Current challenges and future research directions to improve the understanding of severe haze pollution as well as plausible regulatory implications on a scientific basis are also discussed.

https://www.pnas.org/content/pnas/116/18/8657.full.pdf

Severe haze in northern China: A synergy of anthropogenic emissions and atmospheric processes.

Although much attention has been paid to investigating and controlling air pollution in China, the trends of air-pollutant concentrations on a national scale have remained unclear. Here, we quantitatively investigated the variation of air pollutants in China using long-term comprehensive data sets from 2013 to 2017, during which Chinese government made major efforts to reduce anthropogenic emission in polluted regions. Our results show a significant decreasing trend in the PM2.5 concentration in heavily polluted regions of eastern China, with an annual decrease of ∼7% compared with measurements in 2013. The measured decreased concentrations of SO2, NO2 and CO (a proxy for anthropogenic volatile organic compounds) could explain a large fraction of the decreased PM2.5 concentrations in different regions. As a consequence, the heavily polluted days decreased significantly in corresponding regions. Concentrations of organic aerosol, nitrate, sulfate, ammonium and chloride measured in urban Beijing revealed a remarkable reduction from 2013 to 2017, connecting the decreases in aerosol precursors with corresponding chemical components closely. However, surface-ozone concentrations showed increasing trends in most urban stations from 2013 to 2017, which indicates stronger photochemical pollution. The boundary-layer height in capital cities of eastern China showed no significant trends over the Beijing-Tianjin-Hebei, Yangtze River Delta and Pearl River Delta regions from 2013 to 2017, which confirmed the reduction in anthropogenic emissions. Our results demonstrated that the Chinese government was successful in the reduction of particulate matter in urban areas from 2013 to 2017, although the ozone concentration has increased significantly, suggesting a more complex mechanism of improving Chinese air quality in the future.

/pdf/contrasting-trends-of-pm2-5-and-surface-ozone-concentrations-1vf1fdgnx5.pdf

Contrasting trends of PM2.5 and surface-ozone concentrations in China from 2013 to 2017

. Current estimates of agricultural ammonia (NH3) emissions in China differ by more than a factor of 2, hindering our understanding of their environmental consequences. Here we apply both bottom-up statistical and top-down inversion methods to quantify NH3 emissions from agriculture in China for the year 2008. We first assimilate satellite observations of NH3 column concentration from the Tropospheric Emission Spectrometer (TES) using the GEOS-Chem adjoint model to optimize Chinese anthropogenic NH3 emissions at the 1∕2°  ×  2∕3° horizontal resolution for March–October 2008. Optimized emissions show a strong summer peak, with emissions about 50 % higher in summer than spring and fall, which is underestimated in current bottom-up NH3 emission estimates. To reconcile the latter with the top-down results, we revisit the processes of agricultural NH3 emissions and develop an improved bottom-up inventory of Chinese NH3 emissions from fertilizer application and livestock waste at the 1∕2°  ×  2∕3° resolution. Our bottom-up emission inventory includes more detailed information on crop-specific fertilizer application practices and better accounts for meteorological modulation of NH3 emission factors in China. We find that annual anthropogenic NH3 emissions are 11.7 Tg for 2008, with 5.05 Tg from fertilizer application and 5.31 Tg from livestock waste. The two sources together account for 88 % of total anthropogenic NH3 emissions in China. Our bottom-up emission estimates also show a distinct seasonality peaking in summer, consistent with top-down results from the satellite-based inversion. Further evaluations using surface network measurements show that the model driven by our bottom-up emissions reproduces the observed spatial and seasonal variations of NH3 gas concentrations and ammonium (NH4+) wet deposition fluxes over China well, providing additional credibility to the improvements we have made to our agricultural NH3 emission inventory.

/pdf/agricultural-ammonia-emissions-in-china-reconciling-bottom-10ro14suwe.pdf

Agricultural ammonia emissions in China: reconciling bottom-up and top-down estimates

. pH is an important property of aerosol particles but is difficult to measure directly. Several studies have estimated the pH values for fine particles in northern China winter haze using thermodynamic models (i.e., E-AIM and ISORROPIA) and ambient measurements. The reported pH values differ widely, ranging from close to 0 (highly acidic) to as high as 7 (neutral). In order to understand the reason for this discrepancy, we calculated pH values using these models with different assumptions with regard to model inputs and particle phase states. We find that the large discrepancy is due primarily to differences in the model assumptions adopted in previous studies. Calculations using only aerosol-phase composition as inputs (i.e., reverse mode) are sensitive to the measurement errors of ionic species, and inferred pH values exhibit a bimodal distribution, with peaks between −2 and 2 and between 7 and 10, depending on whether anions or cations are in excess. Calculations using total (gas plus aerosol phase) measurements as inputs (i.e., forward mode) are affected much less by these measurement errors. In future studies, the reverse mode should be avoided whereas the forward mode should be used. Forward-mode calculations in this and previous studies collectively indicate a moderately acidic condition (pH from about 4 to about 5) for fine particles in northern China winter haze, indicating further that ammonia plays an important role in determining this property. The assumed particle phase state, either stable (solid plus liquid) or metastable (only liquid), does not significantly impact pH predictions. The unrealistic pH values of about 7 in a few previous studies (using the standard ISORROPIA model and stable state assumption) resulted from coding errors in the model, which have been identified and fixed in this study.

/pdf/fine-particle-ph-for-beijing-winter-haze-as-inferred-from-p1k9e6hx5v.pdf

Fine-particle pH for Beijing winter haze as inferred from different thermodynamic equilibrium models

The reduction of ammonia (NH3) emissions is urgently needed due to its role in aerosol nucleation and growth causing haze formation during its conversion into ammonium (NH4(+)). However, the relative contributions of individual NH3 sources are unclear, and debate remains over whether agricultural emissions dominate atmospheric NH3 in urban areas. Based on the chemical and isotopic measurements of size-resolved aerosols in urban Beijing, China, we find that the natural abundance of (15)N (expressed using δ(15)N values) of NH4(+) in fine particles varies with the development of haze episodes, ranging from -37.1‰ to -21.7‰ during clean/dusty days (relative humidity: ∼ 40%), to -13.1‰ to +5.8‰ during hazy days (relative humidity: 70-90%). After accounting for the isotope exchange between NH3 gas and aerosol NH4(+), the δ(15)N value of the initial NH3 during hazy days is found to be -14.5‰ to -1.6‰, which indicates fossil fuel-based emissions. These emissions contribute 90% of the total NH3 during hazy days in urban Beijing. This work demonstrates the analysis of δ(15)N values of aerosol NH4(+) to be a promising new tool for partitioning atmospheric NH3 sources, providing policy makers with insights into NH3 emissions and secondary aerosols for regulation in urban environments.

Fossil Fuel Combustion-Related Emissions Dominate Atmospheric Ammonia Sources during Severe Haze Episodes: Evidence from 15 N-Stable Isotope in Size-Resolved Aerosol Ammonium

B. Zheng

Papers

Fossil Fuel Combustion-Related Emissions Dominate Atmospheric Ammonia Sources during Severe Haze Episodes: Evidence from 15 N-Stable Isotope in Size-Resolved Aerosol Ammonium