Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions as well as two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r² = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH₂SO₂⁺) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size distributions, oxidation states of OA and evolutionary processes of secondary aerosols.

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 (SO₂) emitted by coal combustion. There has been considerable debate regarding the mechanism for SO₂ oxidation. Here we show evidence from field observations of a haze event that rapid oxidation of SO₂ by nitrogen dioxide (NO₂) and nitrous acid (HONO) takes place, the latter producing nitrous oxide (N₂O). 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 SO₂ by NO₂, producing HONO which can in turn oxidize SO₂ to yield N₂O.This mechanism could provide an explanation for sulfate formation under some winter haze conditions.

Air quality has been continuously improved in recent years in Beijing, yet severe haze episodes still frequently occur in winter. Here we deployed an Aerodyne high‐resolution aerosol mass spectrometer in two winter seasons during the same period to investigate the changes in aerosol chemistry from 2014 to 2016 in Beijing. Compared to 2014, submicron aerosol (PM₁) species showed ubiquitous increases in mass concentrations by 10–130% in winter 2016, of which nitrate showed the largest increase among all aerosol species leading to a much higher NO₃/SO₄ ratio in 2016 (1.36 ± 0.90) than 2014 (0.72 ± 0.59). This result highlights an increasing role of nitrate in particulate matter pollution in recent years in Beijing. Aerosol composition and size distributions also changed significantly. Secondary inorganic species showed elevated contributions by ~10% in winter 2016 associated with corresponding decreases in organic aerosol (OA). Positive matrix factorization of OA illustrated the significant changes in both primary emissions and secondary production. While cooking OA decreased substantially from 25% in 2014 to 15% in 2016, the contribution of biomass burning OA slightly increased instead. Although secondary OA contributed similarly to OA in the two winters (49% vs. 53%), we observed ubiquitous increases (~50%) in photochemically related oxygenated OA and oxidized primary OA, and oxygen‐to‐carbon ratios of OA, indicating the enhanced photochemical production in winter 2016. Aqueous‐phase production of secondary OA however was relatively similar in the two winters. Further analysis demonstrated that the changes in aerosol and OA composition varied differently across different pollution and relative humidity levels.

Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM_2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013–2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat. Significance Secondary organic aerosol (SOA) from fossil-fuel combustion is a major component of Beijing winter haze pollution but its formation mechanisms are unclear. It is generally assumed to originate from atmospheric oxidation of volatile organic compounds (VOCs). However, we show here that fast aqueous-phase oxidation of directly emitted primary organic aerosol (POA) takes place at high relative humidity in Beijing winter haze and can explain the observed SOA. This could explain why SOA has decreased in response to POA emission controls even as VOC emissions have stayed flat. The mechanism may involve ring-breaking oxidation and functionalization of polycyclic aromatic hydrocarbons.

It is a puzzle as to why more severe haze formed during the New Year Holiday in 2020 (NYH‐20), when China was in an unprecedented state of shutdown to contain the coronavirus (COVID‐19) outbreak, than in 2019 (NYH‐19). We performed a comprehensive measurement and modeling analysis of the aerosol chemistry and physics at multiple sites in China (mainly in Shanghai) before, during, and after NYH‐19 and NYH‐20. Much higher secondary aerosol fraction in PM_2.5 were observed during NYH‐20 (73%) than during NYH‐19 (59%). During NYH‐20, PM_2.5 levels correlated significantly with the oxidation ratio of nitrogen (r² = 0.77, p < 0.01), and aged particles from northern China were found to impede atmospheric new particle formation and growth in Shanghai. A markedly enhanced efficiency of nitrate aerosol formation was observed along the transport pathways during NYH‐20, despite the overall low atmospheric NO₂ levels.

A revised Community Multi-scale Air Quality (CMAQ) model with updated secondary organic aerosol (SOA) yields and a more detailed description of SOA formation from isoprene oxidation was applied to study the spatial and temporal distribution of SOA in China in the entire year of 2013. Predicted organic carbon (OC), elemental carbon and volatile organic compounds agreed favorably with observations at several urban areas, although the high OC concentrations in wintertime in Beijing were under-predicted. Predicted summer SOA was generally higher (10–15 µg m⁻³) due to large contributions of isoprene (country average, 61 %), although the relative importance varies in different regions. Winter SOA was slightly lower and was mostly due to emissions of alkane and aromatic compounds (51 %). Contributions of monoterpene SOA was relatively constant (8–10 %). Overall, biogenic SOA accounted for approximately 75 % of total SOA in summer, 50–60 % in autumn and spring, and 24 % in winter. The Sichuan Basin had the highest predicted SOA concentrations in the country in all seasons, with hourly concentrations up to 50 µg m⁻³. Approximately half of the SOA in all seasons was due to the traditional equilibrium partitioning of semivolatile components followed by oligomerization, while the remaining SOA was mainly due to reactive surface uptake of isoprene epoxide (5–14 %), glyoxal (14–25 %) and methylglyoxal (23–28 %). Sensitivity analyses showed that formation of SOA from biogenic emissions was significantly enhanced due to anthropogenic emissions. Removing all anthropogenic emissions while keeping the biogenic emissions unchanged led to total SOA concentrations of less than 1 µg m⁻³, which suggests that manmade emissions facilitated biogenic SOA formation and controlling anthropogenic emissions would result in reduction of both anthropogenic and biogenic SOA.