Influence of organic aerosol molecular composition on particle absorptive properties in autumn Beijing

Publisher Copyright: © 2022 Jing Cai et al.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 μg 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.Peer reviewe

Amplified role of potential HONO sources in O3 formation in North China Plain during autumn haze aggravating processes

Co-occurrences of high concentrations of PM2.5 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 groundbased (traffic, soil, and indoor emissions, and the NO2 heterogeneous reaction on ground surface (Het(ground))) sources, and two aerosol-related (the NO2 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 C OH reaction and aerosol-related HONO sources decreased slowly with height. Photnitrate 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 (similar to 30 %-70% when the ratio of the photolysis frequency of nitrate (J(nitrate)) to gas nitric acid (JHNO(3)) 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 similar to 5% of the surface HONO in the daytime with a J(nitrate) =JHNO(3) ratio of 30 but contributed similar to 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 NOx-sensitive chemistry. Phot(nitrate) had a limited impact on nitrate concentrations (Peer reviewe

Dust emission reduction enhanced gas-to-particle conversion of ammonia in the North China Plain

Liu et al. found that the formation rate of particulate ammonium is slower in the atmosphere than that observed in the laboratory, while it is sped up due to an increase in aerosol acidity driven by an emission reduction of dust in North China Plain.Ammonium salt is an important component of particulate matter with aerodynamic diameter less than 2.5 mu m (PM2.5) and has significant impacts on air quality, climate, and natural ecosystems. However, a fundamental understanding of the conversion kinetics from ammonia to ammonium in unique environments of high aerosol loading is lacking. Here, we report the uptake coefficient of ammonia (gamma(NH3)) on ambient PM2.5 varying from 2.2 x 10(-4) to 6.0 x 10(-4) in the North China Plain. It is significantly lower than those on the model particles under simple conditions reported in the literature. The probability-weighted gamma(NH3) increases obviously, which is well explained by the annual decrease in aerosol pH due to the significant decline in alkali and alkali earth metal contents from the emission source of dust. Our results elaborate on the complex interactions between primary emissions and the secondary formation of aerosols and the important role of dust in atmospheric chemistry.Peer reviewe

Seasonal variation in oxygenated organic molecules in urban Beijing and their contribution to secondary organic aerosol

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 x 10(8) cm(-3)), followed by autumn (7.9 x 10(7) cm(-3)), spring (5.7 x 10(7) cm(-3)) and winter (2.3 x 10(7) 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 (nO(eff) = nO - 2 x 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 x 10(7) cm(-3)) and monoterpene (1.1-8.4 x 10(6) 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 NO, 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 mu 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.Peer reviewe

Influence of Aerosol Chemical Composition on Condensation Sink Efficiency and New Particle Formation in Beijing

Relatively high concentrations of preexisting particles, acting as a condensation sink (CS) of gaseous precursors, have been thought to suppress the occurrence of new particle formation (NPF) in urban environments, yet NPF still occurs frequently. Here, we aim to understand the factors promoting and inhibiting NPF events in urban Beijing by combining one-year-long measurements of particle number size distributions and PM2.5 chemical composition. Our results show that indeed the CS is an important factor controlling the occurrence of NPF events, with its chemical composition affecting the efficiency of the background particles in removing gaseous H2SO4 (effectiveness of the CS) driving NPF. During our observation period, the CS was found to be more effective for ammonium nitrate-rich (NH4NO3-rich) fine particles. On non-NPF event days, particles acting as CS contained a larger fraction of NH4NO3 compared to NPF event days under comparable CS levels. In particular, in the CS range from 0.02 to 0.03 s(-1), the nitrate fraction was 17% on NPF event days and 26% on non-NPF event days. Overall, our results highlight the importance of considering the chemical composition of preexisting particles when estimating the CS and their role in inhibiting NPF events, especially in urban environments.Peer reviewe

Rapid mass growth and enhanced light extinction of atmospheric aerosols during the heating season haze episodes in Beijing revealed by aerosol-chemistry-radiation-boundary layer interaction

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 similar to 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.Peer reviewe

Size-segregated particle number and mass concentrations from different emission sources in urban Beijing

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 mu gm(-3); 2.4 +/- 1.8 x 10(3) cm(-3) and 5.5 +/- 2.8 x 10(3) cm(-3) for two traffic-related components), cooking emissions (2.6 +/- 1.9 mu gm(-3) and 5.5 +/- 3.3 x 10(3) cm(-3)) and secondary aerosols (51 +/- 41 mu gm(-3) and 4.2 +/- 3.0 x 10(3) 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 re-sults 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.Peer reviewe

Unprecedented Ambient Sulfur Trioxide (SO3) Detection : Possible Formation Mechanism and Atmospheric Implications

Sulfur trioxide (SO3) is a crucial compound for atmospheric sulfuric acid (H2SO4) formation, acid rain formation, and other atmospheric physicochemical processes. During the daytime, SO3 is mainly produced from the photo-oxidation of SO2 by OH radicals. However, the sources of SO3 during the early morning and night, when OH radicals are scarce, are not fully understood. We report results from two field measurements in urban Beijing during winter and summer 2019, using a nitrate-CI-APi-LTOF (chemical ionization-atmospheric pressure interface-long-time-offlight) mass spectrometer to detect atmospheric SO3 and H2SO4. Our results show the level of SO3 was higher during the winter than during the summer, with high SO3 levels observed especially during the early morning (similar to 05:00 to similar to 08:30) and night (similar to 18:00 to similar to 05:00 the next day). On the basis of analysis of SO2, NOx, black carbon, traffic flow, and atmospheric ions, we suggest SO3 could be formed from the catalytic oxidation of SO2 on the surface of traffic-related black carbon. This previously unidentified SO3 source results in significant H2SO4 formation in the early morning and thus promotes sub-2.5 nm particle formation. These findings will help in understanding urban SO3 and formulating policies to mitigate secondary particle formation in Chinese megacities.Peer reviewe

Continuous and comprehensive atmospheric observations in Beijing : a station to understand the complex urban atmospheric environment

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