Environmental factors driving the formation of water-soluble organic aerosols: A comparative study under contrasting atmospheric conditions.

Water-soluble organic carbon (WSOC), as major fractions of atmospheric aerosols, have gained attention due to their light-absorption properties. To illustrate the sources and key environmental factors driving WSOC formation under different atmospheric conditions, a comparative study was conducted by summarizing the results obtained from five field campaigns at inland (urban, suburban or regional) sites and a coastal site during different seasons. Organic carbon concentrations varied from 8.5 µg/m3 at the summer regional site to 17.5 µg/m3 at the winter urban site, with 46 %- 89 % of the mass as WSOC. Based on correlation analysis, primary combustion emissions were more important in winter than in summer, and secondary formation was an important source of WSOC during winter, summer and autumn. Atmospheric oxidants (NO2, O3), aerosol liquid water (ALW) and ambient RH were important factors influencing the WSOC formation, while their roles varied in different atmospheres. We observed a seasonal transition of atmospheric oxidants dominating the WSOC formation from O3 and NO2-driven conditions in summer to NO2-driven conditions in winter. Elevated ALW or ambient RH generally favor the WSOC formation, while the WSOC dependence of ALW varied among different ALW ranges. As the increasing of ALW or ambient RH, a transition of WSOC formation from "RH/ALW-limited regime" under low-ALW conditions, to "RH/ALW and precursor-driven regime" under medium-ALW/RH, and to "precursor-limited (RH/ALW-excess) regime" were observed for the inland atmospheric conditions. Under the high-RH and ALW conditions in coastal areas, ALW or ambient RH was generally not a limiting factor for WSOC formation.

Parameterization of the ambient aerosol refractive index with source appointed chemical compositions.

The refractive index of ambient aerosols is widely used in the climate model and remote sensing. Traditionally, the real part of the refractive index (RRI) of the ambient aerosol is calculated from the measured mass fraction of the main inorganic components with known refractive index, without full resolving the effects of variation in the RRI of organic components, which always contribute more than 50 % of the total aerosol mass. For the first time, the ambient aerosol RRI and the aerosol chemical components were measured concurrently at a suburban site Changping, in Beijing, China. Measurements results show that the ambient aerosol ranges between 1.57 and 1.71 with a mean value of 1.66. The mean mass fractions of organic aerosol (OA), nitrate, sulfate, ammonium, and chloride to total non-refractory aerosol loading are 43.1 %, 21.9 %, 21.6 %, 13.1 %, and 0.3 % respectively. Source appointment analysis of the organic aerosol show that the fossil fuel-related OA, cooking OA, biomass burning OA, less oxidized oxygenated OA and more oxidized OOA contributes 18.0 %, 11.2 %, 4.1 %, 39.9 %, 26.7 % to the total aerosol. A new parameterization scheme of the ambient aerosol RRI, which considers the source appointed OA, is proposed based on the concurrent measurements of RRI and chemical composition. The measured and parameterized RRI shows good consistency with a correlation coefficient of 0.79 and slope of 0.98. Our measurement results reveal that a significant deviation of the calculated RRI exists without considering the variation of the RRI of the aerosol organic component. The parametrization scheme is adopted and applicable in aerosol model for bettering estimating the corresponding optical and radiative effects.

Variations in source contributions of particle number concentration under long-term emission control in winter of urban Beijing.

Many studies revealed the rapid decline of atmospheric PM2.5 in Beijing due to the emission control measures. The variation of particle number concentration (PN) which has important influences on regional climate and human health, however, was rarely reported. This study measured the particle number size distributions (PNSD) in 3-700 nm in winter of Beijing during 2013-2019. It was found that PN decreased by 58% from 2013 to 2017, but increased by 29% from 2017 to 2019. By Positive matrix factorization (PMF) analysis, five source factors of PNSD were identified as Nucleation, Fresh traffic, Aged traffic + Diesel, Coal + biomass burning and Secondary. Overall, factors associated with primary emissions were found to decrease continuously. Coal + biomass burning dominated the reduction (65%) among the three primary sources during 2013-2017, which resulted from the great efforts on emission control of coal combustion and biomass burning. Fresh traffic and Aged traffic + Diesel decreased by 43% and 66%, respectively, from 2013 to 2019, as a result of the upgrade of the vehicle emission standards in Beijing-Tianjin-Hebei area. On the other hand, the contribution from Nucleation and Secondary decreased with the reduction of gaseous precursors in 2013-2017, but due to the increased intensity of new particle formation (NPF) and secondary oxidation, they increased by 56% and 70%, respectively, from 2017 to 2019, which led to the simultaneously increase of PN and particle volume concentration. This study indicated that NPF may play an important role in urban atmosphere under continuous air quality improvement.

Historically understanding the spatial distributions of particle surface area concentrations over China estimated using a non-parametric machine learning method.

A non-parametric ensemble model was proposed to estimate the long-term (2015-2019) particle surface area concentrations (SA) over China for the first time on basis of a vilification dataset of measured particle number size distribution. This ensemble model showed excellent cross-validation R2 value (CV R2 = 0.83) as well as a relatively low root-mean-square error (RMSE = 195.0 µm2/cm3). No matter in which year, considerable spatial heterogeneity of SA was found over China with higher SA in Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), and Middle Lower Reaches of Yangtze River (MLYR). From 2015 to 2019, SA significantly decreased in representative city clusters. The reduction rates were 140.1 µm2·cm-3·a-1 in BTH, 110.7 µm2·cm-3·a-1 in Pearl River Delta (PRD), 105.2 µm2·cm-3·a-1 in YRD, and 92.4 µm2·cm-3·a-1 in Sichuan Basin (SCB), respectively. Even though such quick reduction, high SA (ranged from ~800 µm2/cm3 to ~1750 µm2/cm3) during the heavy pollution period (PM2.5 > 75 µg/m3) still existed in the above-mentioned city clusters and may provide rich reaction vessels for multiphase chemistry. A dichotomy of enhanced annual 4th maximum daily 8-h average O3 concentrations (4MDA8 O3) and decreased SA during summertime was found in Shanghai, a representative city of YRD. In Chengdu (SCB), increased 4MDA8 O3 concentration was associated with a synchronous increase of SA from 2017 to 2019. Differently, 4MDA8 O3 concentrations enhanced in Beijing (BTH) and Guangzhou (PRD), while not significant for SA before 2018. This work will greatly deepen our understanding of the historical variation and spatial distributions of SA over China.

Particle hygroscopicity inhomogeneity and its impact on reactive uptake.

Atmospheric particles are important reaction vessels for multiphase chemistry. We conducted a meta-analysis of previous field observations in various environments (includes ocean, urban and rural regions), showing that particle hygroscopicity inhomogeneity (PHI) is ubiquitous for the continental atmospheric particles, in which a considerable part of the particulate matters is hydrophobic (10%-33% on average). However, the effects of PHI in quantifying the uptake process of reactive gases are still unclear. Here, taking N2O5 uptake as an example, we showed that using a laboratory-based parameterization scheme without considering the PHI might result in a misestimation of uptake rate coefficient, especially under low ambient relative humidity (RH). Such misestimation may be caused by the differences of the uptake coefficients, as well as the proportion of surface area concentration (SA) between hydrophilic and hydrophobic particles. We suggested that the PHI should be well-considered in establishing the reactive traces gases heterogeneous uptake parameterizations.

The impact of the atmospheric turbulence-development tendency on new particle formation: a common finding on three continents.

A new mechanism of new particle formation (NPF) is investigated using comprehensive measurements of aerosol physicochemical quantities and meteorological variables made in three continents, including Beijing, China; the Southern Great Plains site in the USA; and SMEAR II Station in Hyytiälä, Finland. Despite the considerably different emissions of chemical species among the sites, a common relationship was found between the characteristics of NPF and the stability intensity. The stability parameter (ζ = Z/L, where Z is the height above ground and L is the Monin-Obukhov length) is found to play an important role; it drops significantly before NPF as the atmosphere becomes more unstable, which may serve as an indicator of nucleation bursts. As the atmosphere becomes unstable, the NPF duration is closely related to the tendency for turbulence development, which influences the evolution of the condensation sink. Presumably, the unstable atmosphere may dilute pre-existing particles, effectively reducing the condensation sink, especially at coarse mode to foster nucleation. This new mechanism is confirmed by model simulations using a molecular dynamic model that mimics the impact of turbulence development on nucleation by inducing and intensifying homogeneous nucleation events.

More Significant Impacts From New Particle Formation on Haze Formation During COVID-19 Lockdown.

During the COVID-19 lockdown in 2020, large-scale industrial and transportation emissions were reduced, but high PM2.5 concentration still occurred. This study investigated the variation of particle number size distribution during the lockdown, and analyzed the characteristics of new particle formation (NPF) events and its potential impact on haze formation. Through measurement conducted in urban Beijing during the first 3 months of 2020, and comparison with year-over-year data, the decrease of primary Aitken-mode particles was observed. However, frequencies, formation rates and growth rates of NPF events remained stable between 2020 and 2019 in the same period. As a result, >25 nm particles produced by NPF events, would play a more important role in serving as the haze formation "seeds" compared to those produced by primary emissions. This finding emphasizes the significance on the understanding of NPF mechanisms when making pollution mitigation policy in the future.

Larger than expected variation range in the real part of the refractive index for ambient aerosols in China.

The real part of the refractive index (RRI) of ambient aerosol, which is widely used in remote sensing and atmospheric models, is one of the key factors determining its particles' optical properties. The characteristics of ambient aerosol RRI in China have not yet been well studied owing to a lack of observations. For the first time, the properties of aerosol RRI were studied based on field measurements in China at four sites with different atmospheres. The results revealed that the measured ambient aerosol RRI varied significantly between 1.36 and 1.78, increasing with the mass ratio of organic components. The scattering coefficient and direct radiative effects of the aerosols were estimated to increase by factors of 2 and 3, respectively, when RRI increased from 1.36 to 1.78. Our results indicate that variation in ambient aerosol RRI should be considered in aerosol and climate models to achieve an accurate estimation of aerosol's radiative impacts.

Explosive Secondary Aerosol Formation during Severe Haze in the North China Plain.

Severe haze events with exceedingly high-levels of fine aerosols occur frequently over the past decades in the North China Plain (NCP), exerting profound impacts on human health, weather, and climate. The development of effective mitigation policies requires a comprehensive understanding of the haze formation mechanisms, including identification and quantification of the sources, formation, and transformation of the aerosol species. Haze evolution in this region exhibits distinct physical and chemical characteristics from clean to polluted periods, as evident from increasing stagnation and relative humidity, but decreasing solar radiation as well as explosive secondary aerosol formation. The latter is attributed to highly elevated concentrations of aerosol precursor gases and is reflected by rapid increases in the particle number and mass concentrations, both corresponding to nonequilibrium chemical processes. Considerable new knowledge has been acquired to understand the processes regulating haze formation, particularly in light of the progress in elucidating the aerosol formation mechanisms. This review synthesizes recent advances in understanding secondary aerosol formation, by highlighting several critical chemical/physical processes, that is, new particle formation and aerosol growth driven by photochemistry and aqueous chemistry as well as the interaction between aerosols and atmospheric stability. Current challenges and future research priorities are also discussed.

Vertical profile of particle hygroscopicity and CCN effectiveness during winter in Beijing: insight into the hygroscopicity transition threshold of black carbon.

The hygroscopicity and ability of aerosol particles to act as cloud condensation nuclei (CCN) is important in determining their lifetime and role in aerosol-cloud interactions, thereby influencing cloud formation and climate. Previous studies have used the aerosol hygroscopic properties measured at the ground to evaluate the influence on cloud formation in the atmosphere, which may introduce uncertainty associated with aerosol hygroscopicity variability with altitude. In this study, the CCN behaviour and hygroscopic properties of daily filter collections of PM2.5 from three different heights (8, 120, 260 m) on a tower in Beijing were determined in the laboratory using water, water/methanol and methanol as the atomization solvents. Whilst there was substantial temporal variability in particle concentration and composition, there was little obvious difference in aerosol CCN and hygroscopic behaviour at different heights, although the planetary boundary layer height (PBLH) reduced to below the tower height during the nighttime, suggesting that use of surface hygroscopicity measurements is sufficient for the estimation of aerosol particle activation in clouds. Additionally, the critical coating thickness (in terms of mass ratio of coating/refractory BC, MRc) defining the BC transition between being hydrophobic to hydrophilic, was determined by combining hygroscopic tandem differential mobility analyser (H-TDMA), centrifugal particle mass analyzer (CPMA) and single particle soot photometer (SP2) measurements. The MRc of 250 nm BC-containing particles increased from a background value of between 0.8 and 1.6 to around 4.6 at the onset of the growth event of nanoparticles, decreasing monotonically back to the background level as the event progressed. This indicates that large particles do not act as an effective pre-existing condensation sink of the hygroscopic vapours during the nanoparticle growth events, leading to the 250 nm BC particles requiring more coating materials to transition between being hydrophobic and hydrophilic. These findings show that large particles may be less important in suppressing the new particle formation and subsequent growth in the atmosphere.

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust.

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem.

Wintertime N2O5 uptake coefficients over the North China Plain.

The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) plays an important role in regulating NOx. The N2O5 uptake coefficient, γ(N2O5), was determined using an iterative box model that was constrained to observational data obtained in suburban Beijing from February to March 2016. The box model determined 2289 individual γ(N2O5) values that varied from <0.001 to 0.02 with an average value of 0.0046 ± 0.0039 (and a median value of 0.0032). We found the derived winter γ(N2O5) values in Beijing were relatively low as compared to values reported in previous field studies conducted during winter in Hong Kong (average value of 0.014) and the eastern U.S. coast (median value of 0.0143). In our study, field evidence of the suppression of γ(N2O5) values due to pNO3- content, organics and the enhancement by aerosol liquid water content (ALWC) is in line with previous laboratory study results. Low ALWC, high pNO3- content, and particle morphology (inorganic core with an organic shell) accounted for the low γ(N2O5) values in the North China Plain (NCP) during wintertime. The field-derived γ(N2O5) values are well reproduced by a revised parameterization method, which includes the aerosol size distribution, ALWC, nitrate and organic coating, suggesting the feasibility of comprehensive parameterization in the NCP during wintertime.

Exploring atmospheric free-radical chemistry in China: the self-cleansing capacity and the formation of secondary air pollution.

Since 1971, it has been known that the atmospheric free radicals play a pivotal role in maintaining the oxidizing power of the troposphere. The existence of the oxidizing power is an important feature of the troposphere to remove primary air pollutants emitted from human beings as well as those from the biosphere. Nevertheless, serious secondary air-pollution incidents can take place due to fast oxidation of the primary pollutants. Elucidating the atmospheric free-radical chemistry is a demanding task in the field of atmospheric chemistry worldwide, which includes two kinds of work: first, the setup of reliable radical detection systems; second, integrated field studies that enable closure studies on the sources and sinks of targeted radicals such as OH and NO3. In this review, we try to review the Chinese efforts to explore the atmospheric free-radical chemistry in such chemical complex environments and the possible link of this fast gas-phase oxidation with the fast formation of secondary air pollution in the city-cluster areas in China.

Size-resolved effective density of submicron particles during summertime in the rural atmosphere of Beijing, China.

Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55g/cm3, on average. The effective particle density distributions were dominated by a mode peaked at around 1.5g/cm3 for 50 to 350nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6g/cm3 for 150, 240, and 350nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth.

Potential of secondary aerosol formation from Chinese gasoline engine exhaust.

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.

Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China.

Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 µgC/m3 and 6.9 ± 2.4 µgC/m3, respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM2.5 samples was 17.0 ± 20.2 ng/m3, indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM2.5 without considering high spatial resolution source data and meteorological parameters.

Chemical and physical properties of biomass burning aerosols and their CCN activity: A case study in Beijing, China.

Biomass burning emits large amounts of both trace gases and particles into the atmosphere. It plays a profound role in regional air quality and climate change. In the present study, an intensive campaign was carried out at an urban site in Beijing, China, in June 2014, which covered the winter wheat harvest season over the North China Plain (NCP). Meanwhile, two evident biomass-burning events were observed. A clear burst in ultrafine particles (below 100nm in diameter, PM1) and subsequent particle growth took place during the events. With the growth of the ultrafine particles, the organic fraction of PM1 increased significantly. The ratio of oxygen to carbon (O:C), which had an average value of 0.23±0.04, did not show an obvious enhancement, indicating that a significant chemical aging process of the biomass-burning aerosols was not observed during the course of events. This finding might have been due to the fact that the biomass-burning events occurred in the late afternoon and grew during the nighttime, which is associated with a low atmospheric oxidation capacity. On average, organics and black carbon (BC) were dominant in the biomass-burning aerosols, accounting for 60±10% and 18±3% of PM1. The high organic and BC fractions led to a significant suppression of particle hygroscopicity. Comparisons among hygroscopicity tandem differential mobility analyzer (HTDMA)-derived, cloud condensation nuclei counter (CCNc)-derived, and aerosol mass spectrometer-based hygroscopicity parameter (κ) values were consistent. The mean κ values of biomass-burning aerosols derived from both HTDMA and CCNc measurements were approximately 0.1, regardless of the particle size, indicating that the biomass-burning aerosols were less active. The burst in particle count during the biomass-burning events resulted in an increased number of cloud condensation nuclei (CCN) at supersaturation (SS)=0.2-0.8%.

New particle formation in China: Current knowledge and further directions.

New particle formation (NPF) studies have been conducted in China since 2004. Formation of new atmospheric aerosol particles has been observed to take place in diverse environments, even under the circumstances of high pre-existing particle loading, challenging the traditional and present understanding of the physicochemical nucleation mechanisms, which have been proposed based on the investigations in clean environments and under laboratory experimental conditions. This paper summarizes the present status and gaps in understanding NPF in China and discusses the main directions opening for future research.

Persistent sulfate formation from London Fog to Chinese haze.

Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH3 and NO2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

Insights into a dust event transported through Beijing in spring 2012: Morphology, chemical composition and impact on surface aerosols.

Multiple approaches were used to investigate the evolution of surface aerosols in Beijing during the passage of a dust event at high altitude, which was from the Gobi areas of southern Mongolia and covered a wide range of North China. Single particle analysis with electron microscope showed that the majority of coarse particles were mineral ones, and most of them were in the size range of 1-7µm with a peak of number concentration at about 3.5µm. Based on elemental composition and morphology, the mineral particles could be classified into several groups, including Si-rich (71%), Ca-rich (15%), Fe-rich (6%), and halite-rich (2%), etc., and they were the main contributors to the aerosol optical depth as the dust occurred. The size distributions of surface aerosols were significantly affected by the dust intrusion. The average number concentration of accumulation mode particles during the event was about 400cm(-3), which was much lower than that in heavily polluted days (6300cm(-3)). At the stage of floating dust, the number concentration of accumulation mode particles decreased, and coarse particles contributed to total volume concentration of particulate matter as much as 90%. The accumulation mode particles collected in this stage were mostly in the size range of 0.2-0.5µm, and were rectangular or spherical. They were considered to be particles consisting of ammonium sulfate. New particle formation (NPF) was observed around noon in the three days during the dust event, indicating that the passage of the dust was probably favorable for NPF.