Multiphase chemistry of NO2 and alkaline matter in aerosol water explains rapid sulfate formation and severe haze in China.

The nationwide extent of surface ozone pollution in China and its comparison to the global ozone distribution have not been recognized because of the scarcity of Chinese monitoring sites before 2012. Here we address this issue by using the latest 5 year (2013–2017) surface ozone measurements from the Chinese monitoring network, combined with the recent Tropospheric Ozone Assessment Report (TOAR) database for other industrialized regions such as Japan, South Korea, Europe, and the United States (JKEU). We use various human health and vegetation exposure metrics. We find that although the median ozone values are comparable between Chinese and JKEU cities, the magnitude and frequency of high-ozone events are much larger in China. The national warm-season (April–September) fourth highest daily maximum 8 h average (4MDA8) ozone level (86.0 ppb) and the number of days with MDA8 values of >70 ppb (NDGT70, 29.7 days) in China are 6.3–30% (range of regional mean differences) and 93–575% higher, respectively, than the JKEU regional averages. Health exposure metrics such as warm-season mean MDA8 and annual SOMO35 (sum of ozone means over 35 ppb) are 6.3–16 and 25–95% higher in China, respectively. We also find an increase in the surface ozone level over China in 2016 and 2017 relative to 2013 and 2014. Our results show that on the regional scale the exposure of humans and vegetation to ozone is greater in China than in other developed regions of the world with comprehensive ozone monitoring.

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.

China’s nationwide ozone monitoring network initiated in 2013 has observed severe surface ozone pollution. This network, combined with the recent Tropospheric Ozone Assessment Report (TOAR) data set, offers a more comprehensive view on global surface ozone distribution and trends. Here, we report quantitative estimates of the warm-season (April–September) surface ozone trends and resulting health impacts at Chinese cities in 2013–2019. Both the parametric and nonparametric linear trends for 12 ozone metrics relevant to human health and vegetation exposure are derived. We find that all ozone metrics averaged from Chinese urban sites have increased significantly since 2013. The warm-season daily maximum 8-h average (MDA8) ozone levels increased by 2.4 ppb (5.0%) year–1, with over 90% of the sites showing positive trends and 30% with trends larger than 3.0 ppb year–1. These rates are among the fastest trends, even faster in some Chinese cities, compared with the urban ozone trends in any other region worldwide reported in TOAR. Ozone metrics reflecting the cumulative exposure effect on human health and vegetation such as SOMO35 and AOT40 have increased at even faster rates (>10% year–1). We estimate that the total premature respiratory mortalities attributable to ambient MDA8 ozone exposure in 69 Chinese cities are 64,370 in 2019, which has increased by 60% compared to 2013 levels and requires urgent attention.

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.