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Peroxyacetyl nitrate (PAN), a key indicator of photochemical pollution, is generated similarly to ozone (O3), through reactions involving specific volatile organic compounds (VOCs) and nitrogen oxides. Notably, PAN has been observed at unexpectedly high concentrations (maximum: 3.04 ppb) during the summertime. The average daily values of PAN show a strong correlation with black carbon (BC) (R = 0.77) and O3 (R = 0.77), suggesting a close connection between summertime haze and photochemical pollution. We addressed the puzzle of summertime PAN formation and its association with aerosol pollution under high-O3 conditions in Xiamen, a coastal city in southeastern China, by analyzing continuous high-temporal-resolution data utilizing box modeling in conjunction with the Master Chemical Mechanism (MCM) model. The MCM model, with an index of agreement (IOA) value of 0.75, effectively investigates PAN formation, performing better during the clean period (R2 : 0.68; slope K : 0.91) than the haze one (R2 : 0.47; slope K : 0.75). Using eXtreme Gradient Boosting (XGBoost), we identified NH3, NO 3- , and PM2.5 as the primary factors for simulation bias. Moreover, the net production rate of PAN becomes negative with PAN constrained, suggesting an unknown compensatory mechanism. Both relative incremental reactivity (RIR) and empirical kinetic modeling approach (EKMA) analyses indicate that PAN formation is VOC-controlled. Controlling emissions of VOCs, particularly alkenes, C5H8, and aromatics, would mitigate PAN pollution. PAN promotes OH and HO2 while inhibiting the formation of O3, RO2, NO, and NO2. This study deepens our comprehension of PAN photochemistry while also offering scientific insights for guiding future PAN pollution control strategies. [ABSTRACT FROM AUTHOR]

Nitrous acid (HONO) is an important precursor of OH radicals which affects not only the sinks of primary air pollutants but also the formation of secondary air pollutants, but its source closure in the atmosphere is still controversial due to a lack of experiment validation. In this study, the HONO budget in Beijing has been analyzed and validated through the coronavirus disease (COVID-19) lockdown event, which resulted in a significant reduction in air pollutant emissions, providing a rare opportunity to understand the HONO budget in the atmosphere. We measured HONO and related pollutants from 1 January to 6 March 2020, which covered the Chinese New Year (CNY) and the COVID-19 lockdown. The average concentration of HONO decreased from 0.97 ± 0.74 ppb before CNY to 0.53 ± 0.44 ppb during the COVID-19 lockdown, accompanied by a sharp drop in NO x and the greatest drop in NO (around 87 %). HONO budget analysis suggests that vehicle emissions were the most important source of HONO during the nighttime (53 ± 17 %) before CNY, well supported by the decline in their contribution to HONO during the COVID-19 lockdown. We found that the heterogeneous conversion of NO 2 on ground surfaces was an important nighttime source of HONO (31 ± 5 %), while that on aerosol surfaces was a minor source (2 ± 1 %). Nitrate photolysis became the most important daytime source during the COVID-19 lockdown compared with that before CNY, resulting from the combined effect of the increase in nitrate and the decrease in NO. Our results indicate that reducing vehicle emissions should be an effective measure for alleviating HONO in Beijing. [ABSTRACT FROM AUTHOR]

During the COVID-19 lockdown, the dramatic reduction of anthropogenic emissions provided a unique opportunity to investigate the effects of reduced anthropogenic activity and primary emissions on atmospheric chemical processes and the consequent formation of secondary pollutants. Here, we utilize comprehensive observations to examine the response of atmospheric new particle formation (NPF) to the changes in the atmospheric chemical cocktail. We find that the main clustering process was unaffected by the drastically reduced traffic emissions, and the formation rate of 1.5 nm particles remained unaltered. However, particle survival probability was enhanced due to an increased particle growth rate (GR) during the lockdown period, explaining the enhanced NPF activity in earlier studies. For GR at 1.5–3 nm, sulfuric acid (SA) was the main contributor at high temperatures, whilst there were unaccounted contributing vapors at low temperatures. For GR at 3–7 and 7–15 nm, oxygenated organic molecules (OOMs) played a major role. Surprisingly, OOM composition and volatility were insensitive to the large change of atmospheric NO x concentration; instead the associated high particle growth rates and high OOM concentration during the lockdown period were mostly caused by the enhanced atmospheric oxidative capacity. Overall, our findings suggest a limited role of traffic emissions in NPF. [ABSTRACT FROM AUTHOR]

The long-term monitoring of atmospheric mercury is an important part of the effective evaluation of the Minamata Convention on Mercury. Gaseous elemental mercury (GEM), along with conventional air pollutants and meteorological parameters, was simultaneously observed in Xiamen, Southeast China, in January and July over the period 2012–2020. GEM concentrations in January were highest in 2015 (4.47 ng m -3) and decreased by 2020 (3.93 ng m -3) , while GEM concentrations in July were highest in 2017 (2.65 ng m -3) and lowest in 2020 (1.56 ng m -3). The temporal variation of GEM was typically characterized by higher concentrations in winter than in summer and in nighttime than in daytime. Bivariate polar plots and the concentration-weighted trajectory (CWT) model were used to identify the source regions of GEM on a local and regional scale. The results indicate that the high GEM concentrations in January 2015 were likely due to a combination of high-level Hg emissions and adverse meteorological conditions. Generalized additive models (GAMs), which use a regression analysis method, were established and applied to investigate the influencing factors on the inter-annual variation of GEM. The factors anthropogenic emissions, meteorological conditions, and transportation explained 37.8%±11.9 %, 31.4%±9.0 %, and 30.8%±9.9 % on average of the variation of GEM concentrations, respectively. There was a positive relationship of daily GEM concentrations with T and RH, mostly linking to natural surface emissions and Hg chemical transformations. The interpretation rate of anthropogenic emissions has significantly decreased since 2012, indicating the effectiveness of emission mitigation measures in reducing GEM concentrations in the study region. [ABSTRACT FROM AUTHOR]

This study investigates the influence of the Chinese New Year (CNY) celebrations on local air quality in Beijing from 2013 through 2019. CNY celebrations include burning of fireworks and firecrackers, which consequently has a significant short-term impact on local air quality. In this study, we bring together comprehensive observations at the newly constructed Aerosol and Haze Laboratory at Beijing University of Chemical Technology – West Campus (BUCT-AHL) and hourly measurements from 12 Chinese government air quality measurement stations throughout the Beijing metropolitan area. These datasets are used together to provide a detailed analysis of air quality during the CNY over multiple years, during which the city of Beijing prohibited the use of fireworks and firecrackers in an effort to reduce air pollution before CNY 2018. Datasets used in this study include particulate matter mass concentrations (PM 2.5 and PM 10), trace gases (NO x , SO 2 , O 3 , and CO), and meteorological variables for 2013–2019; aerosol particle size distributions; and concentrations of sulfuric acid and black carbon for 2018 and 2019. Studying the CNY over several years, which has rarely been done in previous studies, can show trends and effects of societal and policy changes over time, and the results can be applied to study problems and potential solutions of air pollution resulting from holiday celebrations. Our results show that during the 2018 CNY, air pollutant concentrations peaked during the CNY night (for example, PM 2.5 reached a peak around midnight of over 250 µ g cm -3 , compared to values of less than 50 µ g cm -3 earlier in the day). The pollutants with the most notable spikes were sulfur dioxide, particulate matter, and black carbon, which are emitted in burning of fireworks and firecrackers. Sulfuric acid concentration followed the sulfur dioxide concentration and showed elevated overnight concentration. Analysis of aerosol particle number size distribution showed direct emissions of particles with diameters around 100 nm in relation to firework burning. During the 2019 CNY, the pollution levels were somewhat lower (PM 2.5 peaking at around 150 µ g cm -3 on CNY compared to values around 100 µ g cm -3 earlier in the day), and only minor peaks related to firework burning were observed. During both CNYs 2018 and 2019 secondary aerosol formation in terms of particle growth was observed. Meteorological conditions were comparable between these 2 years, suggesting that CNY-related emissions were less in 2019 compared to 2018. During the 7-year study period, it appears that there has been a general decrease in CNY-related emissions since 2016. For example, the peak in PM 2.5 in 2016 was over 600 µ g cm -3 , and in the years following, the peak was less each year, with a peak around 150 µ g cm -3 in 2019. This is indicative of the restrictions and public awareness of the air quality issues having a positive effect on improving air quality during the CNY. Going into the future, long-term observations will offer confirmation for these trends. [ABSTRACT FROM AUTHOR]

Oxygenated organic molecules (OOMs) are crucial for atmospheric new particle formation and secondary organic aerosol (SOA) growth. Therefore, understanding their chemical composition, temporal behavior, and sources is of great importance. Previous studies on OOMs mainly focus on environments where biogenic sources are predominant, yet studies on sites with dominant anthropogenic emissions, such as megacities, have been lacking. Here, we conducted long-term measurements of OOMs, covering four seasons of the year 2019, in urban Beijing. The OOM concentration was found to be the highest in summer (1.6×108 cm -3), followed by autumn (7.9×107 cm -3), spring (5.7×107 cm -3) and winter (2.3×107 cm -3), suggesting that enhanced photo-oxidation together with the rise in temperature promote the formation of OOMs. Most OOMs contained 5 to 10 carbon atoms and 3 to 7 effective oxygen atoms (nOeff=nO-2×nN). The average nO eff increased with increasing atmospheric photo-oxidation capacity, which was the highest in summer and the lowest in winter and autumn. By performing a newly developed workflow, OOMs were classified into the following four types: aromatic OOMs, aliphatic OOMs, isoprene OOMs, and monoterpene OOMs. Among them, aromatic OOMs (29 %–41 %) and aliphatic OOMs (26 %–41 %) were the main contributors in all seasons, indicating that OOMs in Beijing were dominated by anthropogenic sources. The contribution of isoprene OOMs increased significantly in summer (33 %), which is much higher than those in the other three seasons (8 %–10 %). Concentrations of isoprene (0.2– 5.3×107 cm -3) and monoterpene (1.1– 8.4×106 cm -3) OOMs in Beijing were lower than those reported at other sites, and they possessed lower oxygen and higher nitrogen contents due to high NOx levels (9.5–38.3 ppbv – parts per billion by volume) in Beijing. With regard to the nitrogen content of the two anthropogenic OOMs, aromatic OOMs were mainly composed of CHO and CHON species, while aliphatic OOMs were dominated by CHON and CHON2 ones. Such prominent differences suggest varying formation pathways between these two OOMs. By combining the measurements and an aerosol dynamic model, we estimated that the SOA growth rate through OOM condensation could reach 0.64, 0.61, 0.41, and 0.30 µ g m -3 h -1 in autumn, summer, spring, and winter, respectively. Despite the similar concentrations of aromatic and aliphatic OOMs, the former had lower volatilities and, therefore, showed higher contributions (46 %–62 %) to SOA than the latter (14 %–32 %). By contrast, monoterpene OOMs and isoprene OOMs, limited by low abundances or high volatilities, had low contributions of 8 %–12 % and 3 %–5 %, respectively. Overall, our results improve the understanding of the concentration, chemical composition, seasonal variation, and potential atmospheric impacts of OOMs, which can help formulate refined restriction policy specific to SOA control in urban areas. [ABSTRACT FROM AUTHOR]

Co-occurrences of high concentrations of PM 2.5 and ozone (O 3) have been frequently observed in haze-aggravating processes in the North China Plain (NCP) over the past few years. Higher O 3 concentrations on hazy days were hypothesized to be related to nitrous acid (HONO), but the key sources of HONO enhancing O 3 during haze-aggravating processes remain unclear. We added six potential HONO sources, i.e., four ground-based (traffic, soil, and indoor emissions, and the NO 2 heterogeneous reaction on ground surface (Het ground)) sources, and two aerosol-related (the NO 2 heterogeneous reaction on aerosol surfaces (Het aerosol) and nitrate photolysis (Phot nitrate)) sources into the WRF-Chem model and designed 23 simulation scenarios to explore the unclear key sources. The results indicate that ground-based HONO sources producing HONO enhancements showed a rapid decrease with height, while the NO + OH reaction and aerosol-related HONO sources decreased slowly with height. Phot nitrate contributions to HONO concentrations were enhanced with aggravated pollution levels. The enhancement of HONO due to Phot nitrate on hazy days was about 10 times greater than on clean days and Phot nitrate dominated daytime HONO sources (∼ 30 %–70 % when the ratio of the photolysis frequency of nitrate (Jnitrate) to gas nitric acid (JHNO3) equals 30) at higher layers (>800 m). Compared with that on clean days, the Phot nitrate contribution to the enhanced daily maximum 8 h averaged (DMA8) O 3 was increased by over 1 magnitude during the haze-aggravating process. Phot nitrate contributed only ∼ 5 % of the surface HONO in the daytime with a Jnitrate/JHNO3 ratio of 30 but contributed ∼ 30 %–50 % of the enhanced O 3 near the surface in NCP on hazy days. Surface O 3 was dominated by volatile organic compound-sensitive chemistry, while O 3 at higher altitudes (>800 m) was dominated by NO x -sensitive chemistry. Phot nitrate had a limited impact on nitrate concentrations (<15 %) even with a Jnitrate/JHNO3 ratio of 120. These results suggest the potential but significant impact of Phot nitrate on O 3 formation, and that more comprehensive studies on Phot nitrate in the atmosphere are still needed. [ABSTRACT FROM AUTHOR]

Organic aerosol (OA) is a major component of fine particulate matter (PM), affecting air quality, human health, and the climate. The absorptive and reflective behavior of OA components contributes to determining particle optical properties and thus their effects on the radiative budget of the troposphere. There is limited knowledge on the influence of the molecular composition of OA on particle optical properties in the polluted urban environment. In this study, we characterized the molecular composition of oxygenated OA collected on filter samples in the autumn of 2018 in Beijing, China, with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO–CIMS). Three haze episodes occurred during our sampling period with daily maximum concentrations of OA of 50, 30, and 55 µ g m -3. We found that the signal intensities of dicarboxylic acids and sulfur-containing compounds increased during the two more intense haze episodes, while the relative contributions of wood-burning markers and other aromatic compounds were enhanced during the cleaner periods. We further assessed the optical properties of oxygenated OA components by combining detailed chemical composition measurements with collocated particle light absorption measurements. We show that light absorption enhancement (Eabs) of black carbon (BC) was mostly related to more oxygenated OA (e.g., dicarboxylic acids), likely formed in aqueous-phase reactions during the intense haze periods with higher relative humidity, and speculate that they might contribute to lensing effects. Aromatics and nitro-aromatics (e.g., nitrocatechol and its derivatives) were mostly related to a high light absorption coefficient (babs) consistent with light-absorbing (brown) carbon (BrC). Our results provide information on oxygenated OA components at the molecular level associated with BrC and BC particle light absorption and can serve as a basis for further studies on the effects of anthropogenic OA on radiative forcing in the urban environment. [ABSTRACT FROM AUTHOR]

Although the anthropogenic emissions of SO 2 have decreased significantly in China, the decrease in SO 42- in PM 2.5 is much smaller than that of SO 2. This implies an enhanced formation rate of SO 42- in the ambient air, and the mechanism is still under debate. This work investigated the formation mechanism of particulate sulfate based on statistical analysis of long-term observations in Shijiazhuang and Beijing supported with flow tube experiments. Our main finding was that the sulfur oxidation ratio (SOR) was exponentially correlated with ambient RH in Shijiazhuang (SOR = 0.15+0.0032×exp⁡(RH/16.2)) and Beijing (SOR = -0.045+0.12×exp⁡(RH/37.8)). In Shijiazhuang, the SOR is linearly correlated with the ratio of aerosol water content (AWC) in PM 2.5 (SOR = 0.15+0.40×AWC/PM2.5). Our results suggest that uptake of SO 2 instead of oxidation of S(IV) in the particle phase is the rate-determining step for sulfate formation. NH 4 NO 3 plays an important role in the AWC and the change of particle state, which is a crucial factor determining the uptake kinetics of SO 2 and the enhanced SOR during haze days. Our results show that NH 3 significantly promoted the uptake of SO 2 and subsequently the SOR, while NO 2 had little influence on SO 2 uptake and SOR in the presence of NH 3. [ABSTRACT FROM AUTHOR]

Despite the numerous studies investigating haze formation mechanism in China, it is still puzzling that intensive haze episodes could form within hours directly following relatively clean periods. Haze has been suggested to be initiated by the variation of meteorological parameters and then to be substantially enhanced by aerosol–radiation–boundary layer feedback. However, knowledge on the detailed chemical processes and the driving factors for extensive aerosol mass accumulation during the feedback is still scarce. Here, the dependency of the aerosol number size distribution, mass concentration and chemical composition on the daytime mixing layer height (MLH) in urban Beijing is investigated. The size distribution and chemical composition-resolved dry aerosol light extinction is also explored. The results indicate that the aerosol mass concentration and fraction of nitrate increased dramatically when the MLH decreased from high to low conditions, corresponding to relatively clean and polluted conditions, respectively. Particles having their dry diameters in the size of ∼400 –700 nm , and especially particle-phase ammonium nitrate and liquid water, contributed greatly to visibility degradation during the winter haze periods. The dependency of aerosol composition on the MLH revealed that ammonium nitrate and aerosol water content increased the most during low MLH conditions, which may have further triggered enhanced formation of sulfate and organic aerosol via heterogeneous reactions. As a result, more sulfate, nitrate and water-soluble organics were formed, leading to an enhanced water uptake ability and increased light extinction by the aerosols. The results of this study contribute towards a more detailed understanding of the aerosol–chemistry–radiation–boundary layer feedback that is likely to be responsible for explosive aerosol mass growth events in urban Beijing. [ABSTRACT FROM AUTHOR]

Gaseous hydrochloric (HCl) and hydrobromic acid (HBr) are vital halogen species that play essential roles in tropospheric physicochemical processes. Yet, the majority of the current studies on these halogen species were conducted in marine or coastal areas. Detection and source identification of HCl and HBr in inland urban areas remain scarce, thus limiting the full understanding of halogen chemistry and potential atmospheric impacts in the environments with limited influence from the marine sources. Here, both gaseous HCl and HBr were concurrently measured in urban Beijing, China, during winter and early spring of 2019. We observed significant HCl and HBr concentrations ranging from a minimum value at 1 × 10 8 molecules cm -3 (4 ppt) and 4 × 10 7 molecules cm -3 (1 ppt) up to 6 × 10 9 molecules cm -3 (222 ppt) and 1 × 10 9 molecules cm -3 (37 ppt), respectively. The HCl and HBr concentrations are enhanced along with the increase of atmospheric temperature, UVB and levels of gaseous HNO 3. Based on the air mass analysis and high correlations of HCl and HBr with the burning indicators (HCN and HCNO), gaseous HCl and HBr are found to be related to anthropogenic burning aerosols. The gas–particle partitioning may also play a dominant role in the elevated daytime HCl and HBr. During the daytime, the reactions of HCl and HBr with OH radicals lead to significant production of atomic Cl and Br, up to 2 × 10 4 molecules cm -3 s -1 and 8 × 10 4 molecules cm -3 s -1 , respectively. The production rate of atomic Br (via HBr + OH) is 2–3 times higher than that of atomic Cl (via HCl + OH), highlighting the potential importance of bromine chemistry in the urban area. On polluted days, the production rates of atomic Cl and Br are faster than those on clean days. Furthermore, our observations of elevated HCl and HBr may suggest an important recycling pathway of halogen species in inland megacities and may provide a plausible explanation for the widespread halogen chemistry, which could affect the atmospheric oxidation in China. [ABSTRACT FROM AUTHOR]

Secondary aerosols are a major component of PM 2.5 , yet their formation mechanisms in the ambient atmosphere are still unclear. Based on field measurements in downtown Beijing, we show that the photolysis of nitrous acid (HONO) may promote the formation of organic and nitrate aerosols in winter in Beijing, which is supported by the fact that the mass concentrations of organic and nitrate aerosols linearly increase as a function of HONO consumed from early morning to noon. The increased nitrate content also leads to the formation of ammonium particulate matter through enhancing the neutralization of nitrate and sulfate by ammonia. We further illustrate that during pollution events in winter in Beijing, over 50 % of the ambient HONO may be related to traffic-related emissions, including direct emissions and formation via the reaction between OH and vehicle-emitted NO. Overall, our results indicate that traffic-related HONO may play an important role in the oxidative capacity and in turn contribute to haze formation in winter in Beijing. The mitigation of HONO and NO x emissions from vehicles may be an effective way to reduce the formation of secondary aerosols and severe haze events in winter in Beijing. [ABSTRACT FROM AUTHOR]

Although secondary particulate matter is reported to be the main contributor of PM2.5 during haze in Chinese megacities, primary particle emissions also affect particle concentrations. In order to improve estimates of the contribution of primary sources to the particle number and mass concentrations, we performed source apportionment analyses using both chemical fingerprints and particle size distributions measured at the same site in urban Beijing from April to July 2018. Both methods resolved factors related to primary emissions, including vehicular emissions and cooking emissions, which together make up 76 % and 24 % of total particle number and organic aerosol (OA) mass, respectively. Similar source types, including particles related to vehicular emissions (1.6±1.1 µgm-3 ; 2.4±1.8×103 cm-3 and 5.5±2.8×103 cm-3 for two traffic-related components), cooking emissions (2.6±1.9 µgm-3 and 5.5±3.3×103 cm-3) and secondary aerosols (51±41 µgm-3 and 4.2±3.0×103 cm-3), were resolved by both methods. Converted mass concentrations from particle size distributions components were comparable with those from chemical fingerprints. Size distribution source apportionment separated vehicular emissions into a component with a mode diameter of 20 nm ("traffic-ultrafine") and a component with a mode diameter of 100 nm ("traffic-fine"). Consistent with similar day- and nighttime diesel vehicle PM2.5 emissions estimated for the Beijing area, traffic-fine particles, hydrocarbon-like OA (HOA, traffic-related factor resulting from source apportionment using chemical fingerprints) and black carbon (BC) showed similar diurnal patterns, with higher concentrations during the night and morning than during the afternoon when the boundary layer is higher. Traffic-ultrafine particles showed the highest concentrations during the rush-hour period, suggesting a prominent role of local gasoline vehicle emissions. In the absence of new particle formation, our results show that vehicular-related emissions (14 % and 30 % for ultrafine and fine particles, respectively) and cooking-activity-related emissions (32 %) dominate the particle number concentration, while secondary particulate matter (over 80 %) governs PM2.5 mass during the non-heating season in Beijing. [ABSTRACT FROM AUTHOR]