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Clustering of gaseous sulfuric acid (SA) enhanced by dimethylamine (DMA) is a major mechanism for new particle formation (NPF) in polluted atmospheres. However, uncertainty remains regarding the SA–DMA nucleation parameterization that reasonably represents cluster dynamics and is applicable across various atmospheric conditions. This uncertainty hinders accurate three-dimensional (3-D) modeling of NPF and the subsequent assessment of its environmental and climatic impacts. Here we extensively compare different cluster-dynamics-based parameterizations for SA–DMA nucleation and identify the most reliable one through a combination of box model simulations, 3-D modeling, and in situ observations. Results show that the parameterization derived from Atmospheric Cluster Dynamic Code (ACDC) simulations, incorporating the latest theoretical insights (DLPNO-CCSD(T)/aug-cc-pVTZ//ωB97X-D/6-311++G(3df,3pd) level of theory) and adequate representation of cluster dynamics, exhibits dependable performance in 3-D NPF simulation for both winter and summer conditions in Beijing and shows promise for application in diverse atmospheric conditions. Another ACDC-derived parameterization, replacing the level of theory with RI-CC2/aug-cc-pV(T+d)Z//M06-2X/6–311++G(3df,3pd), also performs well in NPF modeling at relatively low temperatures around 280 K but exhibits limitations at higher temperatures due to inappropriate representation of SA–DMA cluster thermodynamics. Additionally, a previously reported parameterization incorporating simplifications is applicable for simulating NPF in polluted atmospheres but tends to overestimate particle formation rates under conditions of elevated temperature (>∼300 K) and low-condensation sink (<∼3×10-3 s−1). Our findings highlight the applicability of the new ACDC-derived parameterization, which couples the latest SA–DMA nucleation theory and holistic cluster dynamics, in 3-D NPF modeling. The ACDC-derived parameterization framework provides a valuable reference for developing parameterizations for other nucleation systems.

In this study, we utilized a 20-bin WRF-Chem (Weather Research and Forecasting coupled with Chemistry) regional model to investigate the contributions of chemical drivers to the growth of new particles, as well as to simulate the three-dimensional dynamics of new particle formation (NPF) events over the North China Plain during a summer campaign in 2019. The model replicated the occurrence of NPF and the growth pattern of newly formed particles, as well as the performance to meet the benchmarks, i.e., absolute mean fractional bias ≤ 50 % and mean fractional error ≤ 75 %, in replicating number concentrations of particles in the 10–40 nm range in five events between 29 June and 6 July 2019. Therefore, we further analyzed three NPF events with distinct particle growth characteristics. In these instances, the model overpredicted daytime condensation of H2SO4 vapor and nighttime formation of NH4NO3. These resulted in overestimation of the hygroscopicity parameter of nanometer particles. Nevertheless, the model performance met the benchmarks for reproducing cloud condensation nuclei (CCN) at a supersaturation (SS) of 0.4 % on NPF days. This was because the overestimation of inorganics was offset by the model underestimation of CCN originating from submicron particles. Additionally, three-dimensional simulations of NPF events demonstrated some key findings. First, NPF consistently begins in the upper parts of the planetary boundary layer (PBL) before expanding. Second, during daytime organics dominate growth of new particles in the PBL, whereas in the free troposphere the primary chemical drivers are inorganic species. However, to confirm these findings, vertical observations are required.

Recent experiments have revealed a vital nucleation process of iodic acid (HIO3) and iodous acid (HIO2) under marine boundary layer conditions. However, HIO3–HIO2 nucleation may not effectively drive the observed rapid new particle formation (NPF) in certain coastal regions influenced by urban air masses. Dimethylamine (DMA) is a promising basic precursor to enhance nucleation considering its strong ability to stabilize acidic clusters and the wide distribution in marine atmosphere, while its role in HIO3–HIO2 nucleation remains unrevealed. Hence, a method combining quantum chemical calculations and Atmospheric Cluster Dynamics Code (ACDC) simulations was utilized to study the HIO3–HIO2–DMA nucleation process. We found that DMA can preferentially accept the proton from HIO3 as a basic precursor in the most stable configurations of HIO3–HIO2–DMA clusters. Kinetically, the participation of DMA in the cluster formation pathways of the iodine oxoacid system could be significant at the 10−1 to 1 pptv level of [DMA]. Furthermore, DMA can enhance the cluster formation rates of the HIO3–HIO2 system in marine and polar regions near DMA sources more than 103-fold. Compared to the classical nucleation mechanism, the HIO3–HIO2–DMA mechanism exhibits strong nucleation ability, worthy of consideration as a promising mechanism in marine and polar regions rich in amine sources. The newly proposed HIO3–HIO2–DMA ternary mechanism might provide an explanation for some missing fluxes of atmospheric iodine particles.

Iodic acid (HIO3) and iodous acid (HIO2) have been identified as nucleating effectively by the Cosmics Leaving Outdoor Droplets (CLOUD) experiment at CERN, yet it may be hard to explain all HIO3-induced nucleation. Given the complexity of marine atmosphere, other precursors may be involved. Methanesulfonic acid (MSA), as a widespread precursor over oceans, has been proven to play a vital role in facilitating nucleation. However, its kinetic impacts on the synergistic nucleation of iodine oxoacids remain unclear. Hence, we investigated the MSA-involved HIO3–HIO2 nucleation process at the molecular level using density functional theory (DFT) and the Atmospheric Cluster Dynamics Code (ACDC). Our results show that MSA can form stable molecular clusters with HIO3 and HIO2 jointed via hydrogen bonds, halogen bonds, and electrostatic attraction after proton transfer to HIO2. Thermodynamically, the MSA-involved clustering can occur nearly without a free-energy barrier, following the HIO2–MSA binary and HIO3–HIO2–MSA ternary pathway. Furthermore, our results show that considering MSA will significantly enhance the calculated rate of HIO3–HIO2-based cluster formation, by up to 104-fold in cold marine regions containing rich MSA and scarce iodine, such as the polar regions Ny-Ålesund and Marambio. Thus, the proposed more efficient HIO3–HIO2–MSA nucleation mechanism may provide theoretical evidence for explaining the frequent and intensive bursts of marine iodine particles.

Soot is a crucial component of aerosols in the atmosphere. Understanding the hygroscopicity of soot particles is important for studying their role as cloud condensation nuclei (CCN) as well as their chemical behavior and atmospheric lifetime. However, there is still a lack of comprehensive understanding regarding the factors that determine the hygroscopic properties of soot. In this work, the hygroscopic behavior of soot particles generated from different types of fuel combustion and aged with SO2 for varying durations was measured by a vapor sorption analyzer. Various characterizations of soot were conducted to understand the key factors that influence the hygroscopic properties of soot. It was found that water-soluble substances in soot facilitate the completion of monolayer water adsorption at low relative humidity and increase the number of water adsorption layers at high relative humidity. On the other hand, soot prepared from fuel burning typically lacks water-soluble inorganic ions, and their hygroscopicity is primarily influenced by organic carbon (OC) and microstructure. Furthermore, the hygroscopicity of soot can be enhanced by the formation of sulfate due to heterogeneous oxidation of SO2. These finding sheds light on the critical factors that affect soot hygroscopicity during water adsorption and allows for estimating the interaction between water molecules and soot particles in a humid atmosphere.

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 NOx 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.

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 (PM2.5 and PM10), trace gases (NOx, SO2, O3, 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, PM2.5 reached a peak around midnight of over 250 µg cm−3, compared to values of less than 50 µg 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 (PM2.5 peaking at around 150 µg cm−3 on CNY compared to values around 100 µg 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 PM2.5 in 2016 was over 600 µg cm−3, and in the years following, the peak was less each year, with a peak around 150 µg 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.

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.

Atmospheric new particle formation (NPF) events have attracted increasing attention for their contribution to the global aerosol number budget and therefore their effects on climate, air quality and human health. NPF events are regarded as a regional phenomenon, occurring over a large area. Most observations of NPF events in Beijing and its vicinity were conducted in populated areas, whereas observations of NPF events on mountaintops with low anthropogenic emissions are still rare in China. The spatial variation of NPF event intensity has not been investigated in detail by incorporating both urban areas and mountain measurements in Beijing. Here, we provide NPF event characteristics in summer 2018 and 2019 at urban Beijing and a comparison of NPF event characteristics – NPF event frequency, formation rate and growth rate – by comparing an urban Beijing site and a background mountain site separated by ∼80 km from 14 June to 14 July 2019, as well as giving insights into the connection between both locations. During parallel measurements at urban Beijing and mountain background areas, although the median condensation sink during the first 2 h of the common NPF events was around 0.01 s−1 at both sites, there were notable differences in formation rates between the two locations (median of 5.42 cm−3 s−1 at the urban site and 1.13 cm−3 s−1 at the mountain site during the first 2 h of common NPF events). In addition, the growth rates in the 7–15 nm range for common NPF events at the urban site (median of 7.6 nm h−1) were slightly higher than those at the mountain site (median of 6.5 nm h−1). To understand whether the observed events were connected, we compared air mass trajectories as well as meteorological conditions at both stations. Favorable conditions for the occurrence of regional NPF events were largely affected by air mass transport. Overall, our results demonstrate a clear inhomogeneity of regional NPF within a distance of ∼100 km, possibly due to the discretely distributed emission sources.

Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

We compare Community Multiscale Air Quality (CMAQ) model predictions with measured nitrous acid (HONO) concentrations in Beijing, China, for December 2015. The model with the existing HONO chemistry in CMAQ severely underestimates the observed HONO concentrations with a normalized mean bias of −97 %. We revise the HONO chemistry in the model by implementing six additional heterogeneous reactions in the model: the reaction of nitrogen dioxide (NO2) on ground surfaces, the reaction of NO2 on aerosol surfaces, the reaction of NO2 on soot surfaces, the photolysis of aerosol nitrate, the nitric acid displacement reaction, and the hydrochloric acid displacement reaction. The model with the revised chemistry substantially increases HONO predictions and improves the comparison with observed data with a normalized mean bias of −5 %. The photolysis of HONO enhances daytime hydroxyl radical by almost a factor of 2. The enhanced hydroxyl radical concentrations compare favorably with observed data and produce additional sulfate via the reaction with sulfur dioxide, aerosol nitrate via the reaction with nitrogen dioxide, and secondary organic aerosols via the reactions with volatile organic compounds. The additional sulfate stemming from revised HONO chemistry improves the comparison with observed concentration; however, it does not close the gap between model prediction and the observation during polluted days.

Although the anthropogenic emissions of SO2 have decreased significantly in China, the decrease in SO42- in PM2.5 is much smaller than that of SO2. This implies an enhanced formation rate of SO42- 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 PM2.5 (SOR = 0.15+0.40×AWC/PM2.5). Our results suggest that uptake of SO2 instead of oxidation of S(IV) in the particle phase is the rate-determining step for sulfate formation. NH4NO3 plays an important role in the AWC and the change of particle state, which is a crucial factor determining the uptake kinetics of SO2 and the enhanced SOR during haze days. Our results show that NH3 significantly promoted the uptake of SO2 and subsequently the SOR, while NO2 had little influence on SO2 uptake and SOR in the presence of NH3.

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.

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 × 108 molecules cm−3 (4 ppt) and 4 × 107 molecules cm−3 (1 ppt) up to 6 × 109 molecules cm−3 (222 ppt) and 1 × 109 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 HNO3. 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 × 104 molecules cm−3 s−1 and 8 × 104 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.

Stressed plants and polymer production can emit many unsaturated volatile organic esters (UVOEs). However, secondary organic aerosol (SOA) formation of UVOEs remains unclear, especially under complex ambient conditions. In this study, we mainly investigated ethyl methacrylate (EM) ozonolysis. Results showed that a substantial increase in secondary H2SO4 particles promoted SOA formation with increasing SO2. An important reason was that the homogeneous nucleation of more H2SO4 at high SO2 level provided greater surface area and volume for SOA condensation. However, increased primary H2SO4 with seed acidity enhanced EM uptake but reduced SOA formation. This was ascribed to the fact that the ozonolysis of more adsorbed EM was hampered with the formation of surface H2SO4 at higher particle acidity. Moreover, the increase in secondary H2SO4 particle via homogeneous nucleation favored to the oligomerization of oxidation products, whereas the increasing of primary H2SO4 with acidity in the presence of seed tended to promote the functionalization conversion products. This study indicated that the role of increased H2SO4 to EM-derived SOA may not be the same under different ambient conditions, which helps to advance our understanding of the complicated roles of H2SO4 in the formation of EM-derived SOA.

Gaseous sulfuric acid (SA) has received a lot of attention for its crucial role in atmospheric new particle formation (NPF). And for this reason, studies until now have mainly focused on daytime SA when most NPF events occur. While daytime SA production is driven by SO2 oxidation of OH radicals of photochemical origin, the formation of SA during nighttime and its potential influence on particle formation remains poorly understood. Here we present evidence for significant nighttime SA production in urban Beijing during winter, yielding concentrations between 1.0 and 3.0 × 106 cm−3. We found a high frequency (∼ 30 %) of nighttime SA events, which are defined by the appearance of a distinct SA peak observed between 20:00 and 04:00 local time, with the maximum concentration exceeding 1.0 × 106 cm−3. These events mostly occurred during unpolluted nights with a low vapor condensation sink. Furthermore, we found that under very clean conditions (visibility > 16.0 km) with abundant ozone (concentration > 2.0 × 1011 cm−3, ∼ 7 ppb), the overall sink of SA was strongly correlated with the products of O3, alkenes and SO2 concentrations, suggesting that the ozonolysis of alkenes played a major role in nighttime SA formation under such conditions. This is in light of previous studies showing that the ozonolysis of alkenes can form OH radicals and stabilized Criegee intermediates (SCIs), both of which are able to oxidize SO2 and thus lead to SA formation. However, we also need to point out that there exist additional sources of SA under more polluted conditions, which are not investigated in this study. Moreover, there was a strong correlation between SA concentration and the number concentration of sub-3 nm particles on both clean and polluted nights. Different from forest environments, where oxidized biogenic vapors are the main driver of nighttime clustering, our study demonstrates that the formation of nighttime cluster mode particles in urban environments is mainly driven by nighttime SA production.

Atmospheric submicrometer aerosols have a great effect on air quality and human health, while their formation and evolution processes are still not fully understood. Herein, the crucial role of atmospheric oxidation capacity, as characterized by OH exposure dose in the formation and evolution of secondary submicrometer aerosols, was systematically investigated based on a highly time-resolved chemical characterization of PM1 in a southern suburb of Beijing in summertime from 25 July to 21 August 2019. The averaged concentration of PM1 was 19.3 ± 11.3 µg m−3, and nearly half (48.3 %) of the mass was organic aerosols (OAs) during the observation period. The equivalent photochemical age (ta) estimated from the ratios of toluene to benzene was applied to characterize the OH exposure dose of the air mass, in which an observation period with the similar sources and minimal influence of fresh emission was adopted. The relationships of non-refractory PM1 species, OA factors (i.e., one hydrocarbon-like and three oxygenated organic aerosol factors) and elemental compositions (e.g., H∕C, O∕C, N∕C, S∕C, OM∕OC, and OSc) to ta were analyzed in detail. It was found that higher PM1 concentration accompanied longer ta, with an average increase rate of 0.8 µgm-3h-1. Meanwhile, the formation of sulfate and more oxidized oxygenated OA were most sensitive to the increase in ta, and their contributions to PM1 were enhanced from 22 % to 28 % and from 29 % to 48 %, respectively, as ta increased. In addition, OSc and the ratios of O∕C and OM∕OC increased with the increase in ta. These results indicated that photochemical aging is a key factor leading to the evolution of OA and the increase in PM1 in summertime.

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 µg m−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 µg m−3 and 5.5±3.3×103 cm−3) and secondary aerosols (51±41 µg m−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.

Secondary aerosols are a major component of PM2.5, 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 NOx emissions from vehicles may be an effective way to reduce the formation of secondary aerosols and severe haze events in winter in Beijing.

Sulfuric acid has been shown to be a key driver for new particle formation and subsequent growth in various environments, mainly due to its low volatility. However, direct measurements of gas-phase sulfuric acid are oftentimes not available, and the current sulfuric acid proxies cannot predict, for example, its nighttime concentrations or result in significant discrepancies with measured values. Here, we define the sources and sinks of sulfuric acid in different environments and derive a new physical proxy for sulfuric acid to be utilized in locations and during periods when it is not measured. We used H2SO4 measurements from four different locations: Hyytiälä, Finland; Agia Marina, Cyprus; Budapest, Hungary; and Beijing, China, representing semi-pristine boreal forest, rural environment in the Mediterranean area, urban environment and heavily polluted megacity, respectively. The new proxy takes into account the formation of sulfuric acid from SO2 via OH oxidation and other oxidation pathways, specifically via stabilized Criegee intermediates. The sulfuric acid sinks included in the proxy are its condensation sink (CS) and atmospheric clustering starting from H2SO4 dimer formation. Indeed, we found that the observed sulfuric acid concentration can be explained by the proposed sources and sinks with similar coefficients in the four contrasting environments where we have tested it. Thus, the new proxy is a more flexible and an important improvement over previous proxies. Following the recommendations in this paper, a proxy for a specific location can be derived.

Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 ∘C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 ∘C to 0.7 % at −50 ∘C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at −50 ∘C compared with 25 ∘C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles ( nm) from sulfuric acid remain poorly measured. Therefore, the effect of stabilizing bases, the contribution of ions and the impact of attractive forces on molecular collisions are under debate. Here, we present precise growth rate measurements of uncharged sulfuric acid particles from 1.8 to 10 nm, performed under atmospheric conditions in the CERN (European Organization for Nuclear Research) CLOUD chamber. Our results show that the evaporation of sulfuric acid particles above 2 nm is negligible, and growth proceeds kinetically even at low ammonia concentrations. The experimental growth rates exceed the hard-sphere kinetic limit for the condensation of sulfuric acid. We demonstrate that this results from van der Waals forces between the vapour molecules and particles and disentangle it from charge–dipole interactions. The magnitude of the enhancement depends on the assumed particle hydration and collision kinetics but is increasingly important at smaller sizes, resulting in a steep rise in the observed growth rates with decreasing size. Including the experimental results in a global model, we find that the enhanced growth rate of sulfuric acid particles increases the predicted particle number concentrations in the upper free troposphere by more than 50 %.

The spatial and temporal variability of the number size distribution of aerosol particles is an indicator of the dynamic behavior of Beijing's atmospheric pollution cocktail. This variation reflects the strength of different primary and secondary sources, such as traffic and new particle formation, as well as the main processes affecting the particle population. In this paper, we report size-segregated particle number concentrations observed at a newly developed Beijing station during the winter of 2018. Our measurements covered particle number size distributions over the diameter range of 1.5 nm–1 µm (cluster mode, nucleation mode, Aitken mode and accumulation mode), thus being descriptive of a major fraction of the processes taking place in the atmosphere of Beijing. Here we focus on explaining the concentration variations in the observed particle modes, by relating them to the potential aerosol sources and sinks, and on understanding the connections between these modes. We considered haze days and new particle formation event days separately. Our results show that during the new particle formation (NPF) event days increases in cluster mode particle number concentration were observed, whereas during the haze days high concentrations of accumulation mode particles were present. There was a tight connection between the cluster mode and nucleation mode on both NPF event and haze days. In addition, we correlated the particle number concentrations in different modes with concentrations of trace gases and other parameters measured at our station. Our results show that the particle number concentration in all the modes correlated with NOx, which reflects the contribution of traffic to the whole submicron size range. We also estimated the contribution of ion-induced nucleation in Beijing, and we found this contribution to be negligible.

The heterogeneous reactions of SO2 in the presence of NO2 and C3H6 on TiO2 were investigated with the aid of in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) under dark conditions or with UV–Vis irradiation. Sulfate formation with or without the coexistence of NO2 and/or C3H6 was analyzed with ion chromatography (IC). Under dark conditions, SO2 reacting alone resulted in sulfite formation on TiO2, while the presence of parts per billion (ppb) levels of NO2 promoted the oxidation of SO2 to sulfate. The presence of C3H6 had little effect on sulfate formation in the heterogeneous reaction of SO2 but suppressed sulfate formation in the heterogeneous reaction of SO2 and NO2. UV–Vis irradiation could significantly enhance the heterogeneous oxidation of SO2 on TiO2, leading to copious generation of sulfate, while the coexistence of NO2 and/or C3H6 significantly suppressed sulfate formation in experiments with UV–Vis lights. Step-by-step exposure experiments indicated that C3H6 mainly competes for reactive oxygen species (ROS), while NO2 competes with SO2 for both surface active sites and ROS. Meanwhile, the coexistence of NO2 with C3H6 further resulted in less sulfate formation compared to introducing either one of them separately to the SO2–TiO2 reaction system. The results of this study highlighted the complex heterogeneous reaction processes that take place due to the ubiquitous interactions between organic and inorganic species and the need to consider the influence of coexisting volatile organic compounds (VOCs) and other inorganic gases in the heterogeneous oxidation kinetics of SO2.

Gasoline evaporative emissions have become an important anthropogenic source of urban atmospheric volatile organic compounds (VOCs) and secondary organic aerosol (SOA). These emissions have a significant impact on regional air quality, especially in China where car ownership is growing rapidly. However, the contribution of evaporative emissions to secondary aerosol (SA) is not clear in an air pollution complex in which a high concentration of SO2 and NH3 was present. In this study, the effects of SO2 and NH3 on SA formation from unburned gasoline vapor were investigated in a 30 m3 indoor smog chamber. It was found that an increase in SO2 and NH3 concentrations (0–151 and 0–200 ppb, respectively) could linearly promote the formation of SA, which could be enhanced by a factor of 1.6–2.6 and 2.0–2.5, respectively. Sulfate was most sensitive to the SO2 concentration, followed by organic aerosol, which was due not only to the acid catalytic effect, but was also related to the formation of organic sulfur-containing compounds. In the case of an increasing NH3 concentration, ammonium nitrate increased more significantly than organic aerosol, and nitrogen-containing organics were also enhanced, as revealed by the results of positive matrix factorization (PMF) analysis. New particle formation (NPF) and particle size growth were also significantly enhanced in the presence of SO2 and NH3. This work indicates that gasoline evaporative emissions will be a significant source of SA, especially in the presence of high concentrations of SO2 and NH3. Meanwhile, these emissions might also be a potential source of sulfur- and nitrogen-containing organics. Our work provides a scientific basis for the synergistic emission reduction of secondary aerosol precursors, including NOx, SO2, NH3, and particularly VOCs, to mitigate particulate matter (PM) pollution in China.

Gaseous sulfuric acid (H2SO4) is known as one of the key precursors for atmospheric new particle formation (NPF) processes, but its measurement remains challenging. Therefore, a proxy method that is able to derive gaseous sulfuric acid concentrations from parameters that can be measured relatively easily and accurately is highly desirable for the atmospheric chemistry community. Although such methods are available for clean atmospheric environments, a proxy that works well in a polluted atmosphere, such as that found in Chinese megacities, is yet to be developed. In this study, the gaseous sulfuric acid concentration was measured in February–March 2018, in urban Beijing using a nitrate based – long time-of-flight chemical ionization mass spectrometer (LToF-CIMS). A number of atmospheric parameters were recorded concurrently including the ultraviolet radiation B (UVB) intensity, the concentrations of O3, NOx (sum of NO and NO2), SO2, and HONO, and aerosol particle number size distributions. A proxy for atmospheric daytime gaseous sulfuric acid concentration was derived via a statistical analysis method using the UVB intensity, [SO2], the condensation sink (CS), [O3], and [HONO] (or [NOx]) as the predictor variables, where square brackets denote the concentrations of the corresponding species. In this proxy method, we considered the formation of gaseous sulfuric acid from reactions of SO2 and OH radicals during the daytime, and the loss of gaseous sulfuric acid due to its condensation onto the preexisting particles. In addition, we explored the formation of OH radicals from the conventional gas-phase photochemistry using O3 as a proxy and from the photolysis of HONO using HONO (and subsequently NOx) as a proxy. Our results showed that the UVB intensity and [SO2] are dominant factors in the production of gaseous sulfuric acid, and that the simplest proxy could be constructed with the UVB intensity and [SO2] alone. When the OH radical production from both homogenously and heterogeneously formed precursors were considered, the relative errors were reduced by up to 20 %.

New particle formation (NPF) studies in China were summarized comprehensively in this paper. NPF frequency, formation rate, and particle growth rate were closely compared among the observations carried out at different types of sites in different regions of China in different seasons, with the aim of exploring the nucleation and particle growth mechanisms. The interactions between air pollution and NPF are discussed, emphasizing the properties of NPF under heavy pollution conditions. The current understanding of NPF cannot fully explain the frequent occurrence of NPF at high aerosol loadings in China, and possible reasons for this phenomenon are proposed. The effects of NPF and some aspects of NPF research requiring further investigation are also summarized in this paper.

The effects of SO2 and NH3 on secondary organic aerosol formation have rarely been investigated together, while the interactive effects between inorganic and organic species under highly complex pollution conditions remain uncertain. Here we studied the effects of SO2 and NH3 on secondary aerosol formation in the photooxidation system of toluene∕NOx in the presence or absence of Al2O3 seed aerosols in a 2 m3 smog chamber. The presence of SO2 increased new particle formation and particle growth significantly, regardless of whether NH3 was present. Sulfate, organic aerosol, nitrate, and ammonium were all found to increase linearly with increasing SO2 concentrations. The increases in these four species were more obvious under NH3-rich conditions, and the generation of nitrate, ammonium, and organic aerosol increased more significantly than sulfate with respect to SO2 concentration, while sulfate was the most sensitive species under NH3-poor conditions. The synergistic effects between SO2 and NH3 in the heterogeneous process contributed greatly to secondary aerosol formation. Specifically, the generation of NH4NO3 was found to be highly dependent on the surface area concentration of suspended particles, and increased most significantly with SO2 concentration among the four species under NH3-rich conditions. Meanwhile, the absorbed NH3 might provide a liquid surface layer for the absorption and subsequent reaction of SO2 and organic products and, therefore, enhance sulfate and secondary organic aerosol (SOA) formation. This effect mainly occurred in the heterogeneous process and resulted in a significantly higher growth rate of seed aerosols compared to without NH3. By applying positive matrix factorisation (PMF) analysis to the AMS data, two factors were identified for the generated SOA. One factor, assigned to less-oxidised organic aerosol and some oligomers, increased with increasing SO2 under NH3-poor conditions, mainly due to the well-known acid catalytic effect of the acid products on SOA formation in the heterogeneous process. The other factor, assigned to the highly oxidised organic component and some nitrogen-containing organics (NOC), increased with SO2 under a NH3-rich environment, with NOC (organonitrates and NOC with reduced N) contributing most of the increase.

Brucellosis is one of the most common zoonotic infections in the world. Human infections are the result of direct exposure to infected animals or ingestion of unprocessed dairy products. While Brucella sp. infection has largely been eliminated from commercial cattle and swine with aggressive vaccination, there is a significant prevalence of Brucella sp. infection in the expanding population of feral swine in the US. We report the surgical treatment of a ruptured mycotic aneurysm of the abdominal aorta due to Brucella suis in a woman living in a rural community with a large population of feral swine. Vascular surgeons should be aware that brucellosis can result in arterial infection and should be considered in the differential diagnosis in patients with a history of exposure to feral swine or the ingestion of unprocessed dairy products. [ABSTRACT FROM AUTHOR]