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The formation mechanism of aerosol sulfate during wintertime haze events in China is still largely unknown. As companions, SO 2 and transition metals are mainly emitted from coal combustion. Here, we argue that the transition metal-catalyzed oxidation of SO 2 on aerosol surfaces could be the dominant sulfate formation pathway and investigate this hypothesis by integrating chamber experiments, numerical simulations and in-field observations. Our analysis shows that the contribution of the manganese-catalyzed oxidation of SO 2 on aerosol surfaces is approximately one to two orders of magnitude larger than previously known routes, and contributes 69.2% ± 5.0% of the particulate sulfur production during haze events. This formation pathway could explain the missing source of sulfate and improve the understanding of atmospheric chemistry and climate change. Sulfate aerosols are an important component of wintertime haze events in China, but their production mechanisms are not well known. Here, the authors show that transition metal-catalyzed oxidation of SO 2 on aerosol surfaces could be the dominant sulfate formation pathway in Northern China.

Severe events of wintertime particulate air pollution in Beijing (winter haze) are associated with high relative humidity (RH) and fast production of particulate sulfate from the oxidation of sulfur dioxide (SO 2 ) emitted by coal combustion. There has been considerable debate regarding the mechanism for SO 2 oxidation. Here we show evidence from field observations of a haze event that rapid oxidation of SO 2 by nitrogen dioxide (NO 2 ) and nitrous acid (HONO) takes place, the latter producing nitrous oxide (N 2 O). Sulfate shifts to larger particle sizes during the event, indicative of fog/cloud processing. Fog and cloud readily form under winter haze conditions, leading to high liquid water contents with high pH (>5.5) from elevated ammonia. Such conditions enable fast aqueous-phase oxidation of SO 2 by NO 2 , producing HONO which can in turn oxidize SO 2 to yield N 2 O.This mechanism could provide an explanation for sulfate formation under some winter haze conditions. How sulfur dioxide emitted through coal combustion is oxidized to sulfate particles during winter haze pollution events has been the subject of debate. Here, the authors show that rapid oxidation takes place by nitrogen dioxide and nitrous acid, producing nitrous oxide together with sulfate.

The concentration of fine particulate matter (PM 2.5 ) across China has decreased by 30–50% over the period 2013–2018 due to stringent emission controls. However, the nitrate component of PM 2.5 has not responded effectively to decreasing emissions of nitrogen oxides and has actually increased during winter haze pollution events in the North China Plain. Here, we show that the GEOS-Chem atmospheric chemistry model successfully simulates the nitrate concentrations and trends. We find that winter mean nitrate would have increased over 2013–2018 were it not for favourable meteorology. The principal cause of this nitrate increase is weaker deposition. The fraction of total inorganic nitrate as particulate nitrate instead of gaseous nitric acid over the North China Plain in winter increased from 90% in 2013 to 98% in 2017, as emissions of nitrogen oxides and sulfur dioxide decreased while ammonia emissions remained high. This small increase in the particulate fraction greatly slows down deposition of total inorganic nitrate and hence drives the particulate nitrate increase. Our results suggest that decreasing ammonia emissions would decrease particulate nitrate by driving faster deposition of total inorganic nitrate. Decreasing nitrogen oxide emissions is less effective because it drives faster oxidation of nitrogen oxides and slower deposition of total inorganic nitrate. Reduction of ammonia emissions may be effective in reducing the nitrate component of fine particulate matter air pollution across the North China Plain, according to the simulation of nitrate trends using the GEOS-Chem atmospheric chemistry model.

Severe haze episodes have occurred frequently in the Seoul metropolitan area (SMA) and throughout East Asian countries, especially during winter and early spring. Although notable progress has been attained in understanding these issues, the causes of severe haze formation have not yet been fully investigated. SMA haze is especially difficult to understand, because the area is impacted by both local emissions from anthropogenic and biogenic activities and emissions transported from upwind sources. Here, we investigated the emission sources and formation processes of particulate matter (PM) during three haze episodes measured in early spring of 2019, from 22 February to 2 April, using a high-resolution aerosol mass spectrometer (HR-AMS). Overall, the average concentration of nonrefractory submicron aerosol (NR-PM1) + BC (black carbon) was 35.1 µg m−3, which was composed of 38 % organics, 12 % SO4, 30 % NO3, 13 % NH4, and 5 % BC. The organics had an average oxygen-to-carbon ratio (O∕C) of 0.52 and an average organic mass to organic carbon ratio (OM∕OC) of 1.86. Seven distinct sources of organic aerosols (OAs) were identified via positive matrix factorization (PMF) analysis of the HR-AMS data: vehicle-emitted hydrocarbon-like OA (HOA), cooking OA (COA), solid-fuel-burning emitted OA (SFOA), and four different types of oxidized secondary OA with varying oxidation degrees and temporal trends. Of the 40 d of the measurement period, 23 were identified as haze days (daily average: >35 µg m−3), during which three severe haze episodes were recorded. In particular, PM1 concentration exceeded 100 µg m−3 during the first episode when an alert was issued, and strict emission controls were implemented in the SMA. Our results showed that nitrate dominated during the three haze episodes and accounted for 39 %–43 % of the PM1 concentration on average (vs. 21 %–24 % during the low-loading period), for which there were indications of regional-transport influences. Two regional-transport-influenced oxidized organic aerosols (OOAs), i.e., less oxidized OOA2 (LO-OOA2) and more oxidized OOA2 (MO-OOA2), contributed substantially to the total PM1 during the haze period (12 %–14 % vs. 7 % during the low-loading period), as well. In contrast, HOA and COA only contributed little (4 %–8 % vs. 4 %–6 % during the low-loading period) to the PM1 concentration during the haze days, indicating that local emissions were likely not the main reason for the severe haze issues. Hence, from simultaneous downwind (SMA) and upwind (Beijing) measurements using HR-AMS and ACSM (aerosol chemical speciation monitor) over the same period, the temporal variations in PM1 and each chemical species showed peak values on the order of Beijing (upwind) to the SMA for approximately 2 d. Furthermore, lead (Pb) derived from HR-AMS measurements was observed to increase significantly during the haze period and showed good correlations with MO-OOA2 and LO-OOA2, which is consistent with regional sources. A multiple linear regression model indicated that the transported regionally processed air masses contributed significantly to Pb in the SMA (31 %), especially during the haze period, although local burning was also important by contributing 38 %. The above results suggest that regional transport of polluted air masses might have played an important role in the formation of the haze episodes in the SMA during early spring.

Growth of fine aerosol particles is investigated during the Aerosol-CCN-Cloud Closure Experiment campaign in June 2013 at an urban site near Beijing. Analyses show a high frequency （- 50%） of fine aerosol particle growth events, and show that the growth rates range from 2.1 to 6.5 nm h-1 with a mean value of - 5.1 nm h-1. A review of previous studies indicates that at least four mechanisms can affect the growth of fine aerosol particles： vapor condensation, intramodal coagulation, extramodal coagulation, and multi-phase chemical reaction. At the initial stage of fine aerosol particle growth, condensational growth usually plays a major role and coagulation efficiency generally increases with particle sizes. An overview of previous studies shows higher growth rates over megacity, urban and boreal forest regions than over rural and oceanic regions. This is most likely due to the higher condensational vapor, which can cause strong condensational growth of fine aerosol particles. Associated with these multiple factors of influence, there are large uncertainties for the aerosol particle growth rates, even at the same location.

Dust aerosols play key roles in affecting regional and global climate through their direct, indirect, and semi-direct effects. Dust events have decreased rapidly since the 1980s in East Asia, particularly over northern China, primarily because of changes in meteorological parameters (e.g. surface wind speed and precipitation). In this study, we found that winter (December–January–February) Arctic amplification associated with weakened temperature gradients along with decreased zonal winds is primarily responsible for the large decline in following spring (March–April–May) dust event occurrences over northern China since the mid-1980s. A dust index was developed for northern China by combining the daily frequency of three types of dust event (dust storm, blowing dust, and floating dust). Using the empirical orthogonal function (EOF) analysis, the first pattern of dust events was obtained for spring dust index anomalies, which accounts for 56.2% of the variability during 1961–2014. Moreover, the enhanced Arctic amplification and stronger Northern Hemisphere annular mode (NAM) in winter can result in the anticyclonic anomalies over Siberia and Mongolia, while cyclonic anomalies over East Europe in spring. These results are significantly correlated with the weakened temperature gradients, increased precipitation and soil moisture, and decreased snow cover extent in the mid-latitude over Northern Hemisphere. Based on the future predictions obtained from the Fifth Climate Models Intercomparison Project (CMIP5), we found that the dust event occurrences may continually decrease over northern China due to the enhanced Arctic amplification in future climate.

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.

Organic aerosols (OA) were studied in Fresno, California, in winter 2010 with an Aerodyne High Resolution Time‐of‐Flight Aerosol Mass Spectrometer (HR‐ToF‐AMS). OA dominated the submicron aerosol mass (average = 67%) with an average concentration of 7.9μg m−3 and a nominal formula of C1H1.59N0.014O0.27S0.00008, which corresponds to an average organic mass‐to‐carbon ratio of 1.50. Three primary OA (POA) factors and one oxygenated OA factor (OOA) representative of secondary OA (SOA) were identified via Positive Matrix Factorization of the high‐resolution mass spectra. The three POA factors, which include a traffic‐related hydrocarbon‐like OA (HOA), a cooking OA (COA), and a biomass burning OA (BBOA) released from residential heating, accounted for an average 57% of the OA mass and up to 80% between 6 – 9 P.M., during which enhanced emissions from evening rush hour traffic, dinner cooking, and residential wood burning were exacerbated by low mixed layer height. The mass‐based size distributions of the OA factors were estimated based on multilinear analysis of the size‐resolved mass spectra of organics. Both HOA and BBOA peaked at ∼140 nm in vacuum aerodynamic diameter (Dva) while OOA peaked at an accumulation mode of ∼460 nm. COA exhibited a unique size distribution with two size modes centering at ∼200 nm and 450 nm respectively. This study highlights the leading roles played by anthropogenic POA emissions, primarily from traffic, cooking and residential heating, in aerosol pollution in Fresno in wintertime. Key Points POA was emitted by three main sources: traffic, cooking, and residential heating POA dominated aerosol composition, especially in ultrafine particles SOA elevated at night, likely influenced by aqueous‐phase processing

Although regional haze adversely affects human health and possibly counteracts global warming from increasing levels of greenhouse gases, the formation and radiative forcing of regional haze on climate remain uncertain. By combining field measurements, laboratory experiments, and model simulations, we show a remarkable role of black carbon (BC) particles in driving the formation and trend of regional haze. Our analysis of long-term measurements in China indicates declined frequency of heavy haze events along with significantly reduced SO₂, but negligibly alleviated haze severity. Also, no improving trend exists for moderate haze events. Our complementary laboratory experiments demonstrate that SO₂ oxidation is efficiently catalyzed on BC particles in the presence of NO₂ and NH₃, even at low SO₂ and intermediate relative humidity levels. Inclusion of the BC reaction accounts for about 90–100% and 30–50%of the sulfate production during moderate and heavy haze events, respectively. Calculations using a radiative transfer model and accounting for the sulfate formation on BC yield an invariant radiative forcing of nearly zero W m−2 on the top of the atmosphere throughout haze development, indicating small net climatic cooling/warming but large surface cooling, atmospheric heating, and air stagnation. This BC catalytic chemistry facilitates haze development and explains the observed trends of regional haze in China. Our results imply that reduction of SO₂ alone is insufficient in mitigating haze occurrence and highlight the necessity of accurate representation of the BC chemical and radiative properties in predicting the formation and assessing the impacts of regional haze.

Natural mineral dust and heavy anthropogenic pollution and its complex interactions cause significant environmental problems in East Asia. Due to restrictions of observing technique, real-time morphological change in Asian dust particles owing to coating process of anthropogenic pollutants is still statistically unclear. Here, we first used a newly developed, single-particle polarization detector and quantitatively investigate the evolution of the polarization property of backscattering light reflected from dust particle as they were mixing with anthropogenic pollutants in North China. The decrease in observed depolarization ratio is mainly attributed to the decrease of aspect ratio of the dust particles as a result of continuous coating processes. Hygroscopic growth of Calcium nitrate (Ca(NO 3 ) 2 ) on the surface of the dust particles played a vital role, particularly when they are stagnant in the polluted region with high RH conditions. Reliable statistics highlight the significant importance of internally mixed, ‘quasi-spherical’ Asian dust particles, which markedly act as cloud condensation nuclei and exert regional climate change.