Atmospheric Particle Hygroscopicity and the Influence by Oxidation State of Organic Aerosols in Urban Beijing

A hygroscopic tandem differentialmobility analyser(H-TDMA)was used to observe the sizeresolved hygroscopic characteristics of submicron particles in January and April 2018 in urban Beijing.The probability distribution of the hygroscopic growth factor(HGF-PDF)in winter and spring usually showed a bimodal pattern,with more hygroscopic mode(MH)being more dominant.The seasonal variation in particle hygroscopicity was related to the origin of air mass,which received polluted southerly air masses in spring and clean northwesterly air masses in winter.Particles showed stronger hygroscopic behaviour during heavy pollution episodes(HPEs)with elevated concentrations of secondary aerosols,especially higher mass fraction of nitrate,which were indicated using the PM2.5(particulate matter with diameter below 2.5μm)mass concentration normalised by CO mass concentration.The hygroscopic parameter(κ)values were calculated using H-TDMA(κhtdma)and chemical composition(κchem).The closure study showed thatκchem was overestimated in winter afternoon when compared withκhtdma,because the organic particle hygroscopic parameter(κorg)was overestimated in the calculations.It was influenced by the presence of a high concentration of hydrocarbon-like organic aerosol(HOA)with a weak water uptake ability.A positive relationship was observed betweenκorg and the ratio of oxygenated organic aerosol(OOA)and HOA,thereby indicating that the strong oxidation state enhanced the hygroscopicity of the particles.This study revealed the effect of local emission sources and secondary aerosol formation processes on particle hygroscopicity,which is of great significance for understanding the pollution formation mechanism in the North China Plain.

Relative Contributions of Boundary-Layer Meteorological Factors to the Explosive Growth of PM2.5 during the Red-Alert Heavy Pollution Episodes in Beijing in December 2016

Based on observations of urban mass concentration of fine particulate matter smaller than 2.5 μm in diameter （PM2.5）, ground meteorological data, vertical measurements of winds, temperature, and relative humidity （RH）, and ECMWF reanalysis data, the major changes in the vertical structures of meteorological factors in the boundary layer （BL） during the heavy aerosol pollution episodes （HPEs） that occurred in winter 2016 in the urban Beijing area were analyzed. The HPEs are divided into two stages： the transport of pollutants under prevailing southerly winds, known as the transport stage （TS）, and the PM2.5 explosive growth and pollution accumulation period characterized by a temperature inversion with low winds and high RH in the lower BL, known as the cumulative stage （CS）. During the TS, a surface high lies south of Beijing, and pollutants are transported northwards. During the CS, a stable BL forms and is characterized by weak winds, temperature inversion, and moisture accumulation. Stable atmospheric stratifica- tion featured with light/calm winds and accumulated moisture （RH 〉 80%） below 250 m at the beginning of the CS is closely associated with the inversion, which is strengthened by the considerable decrease in near-surface air temperat- ure due to the interaction between aerosols and radiation after the aerosol pollution occurs. A significant increase in the PLAM （Parameter Linking Aerosol Pollution and Meteorological Elements） index is found, which is linearly re- lated to PM mass change. During the first 10 h of the CS, the more stable BL contributes approximately 84% of the explosive growth of PM2.5 mass. Additional accumulated near-surface moisture caused by the ground temperature de- crease, weak turbulent diffusion, low BL height, and inhibited vertical mixing of water vapor is conducive to the sec- ondary aerosol formation through chemical reactions, including liquid phase and heterogeneous reactions, which fur- ther increases the PM2.5 concentration levels. The contribution of these reaction mechanisms to the explosive growth of PM2,5 mass during the early CS and subsequent pollution accumulation requires further investigation.

Key features of new particle formation events at background sites in China and their influence on cloud condensation nuclei

Long-term continuous measurements of particle number size distributions with mobility diameter sizes ranging from 3 to 800 nm were pertbrmed to study new particle formation （NPF） events at Shangdianzi （SDZ）, Mt. Tai （TS）, and Lin＇an （LAN） stations representing the background atmospheric conditions in the North China Plain （NCP） Central East China （CEC） and Yangtze River Delta （YRD） regions, respectively. The mean formation rate of 3-nm particles was 6.3, 3.7, and 5.8 cm -3 .s-1, and the mean particle growth rate was 3.6, 6.0, and 6.2 nm. h at SDZ, TS, and LAN, respectively. The NPF, event characteristics at the three sites indicate that there may be a stronger source of low volatile vapors and higher condensational sink of pre-existing particles in the YRD region. The formation rate of NPF events at these sites, as well as the condensation sink, is approximately 10 times higher than some results reported at rural/urban sites in western countries. However, the growth rates appear to be 1 2 times higher. Approximately 12%-17% of all NPF events with nucleated particles grow to a climate- relevant size （〉50 nm）. These kinds of NPF events were normally observed with higher growth rate than the other NPF cases. Generally, the cloud condensation nuclei （CCN） number concentration can be enhanced by approximately a factor of 2 6 on these event days. The mean value of the enhancement factor is lowest at LAN （2-3） and highest at SDZ （-4）. NPF events have also been found to have greater impact on CCN production in China at the regional scale than in the other background sites worldwide.

Aerosol Hygroscopicity during the Haze Red-Alert Period in December 2016 at a Rural Site of the North China Plain

A humidification system was deployed to measure aerosol hygroscopicity at a rural site of the North China Plain during the haze red-alert period 17–22 December 2016. The aerosol scattering coefficients under dry [relative humidity（RH） 〈 30%] and wet（RH in the range of 40%–85%） conditions were simultaneously measured at wavelengths of450, 550, and 700 nm. It is found that the aerosol scattering coefficient and backscattering coefficient increased by only 29% and 10%, respectively when RH went up from 40% to 80%, while the hemispheric backscatter fraction went down by 14%, implying that the aerosol hygroscopicity represented by the aerosol scattering enhancement factor f（RH） is relatively low and RH exerted little effects on the aerosol light scattering in this case. The scattering enhancement factors do not show significant differences at the three wavelengths, only with an approximate 2% variation, suggesting that the aerosol hygroscopicity is independent of the wavelength. Aerosol hygroscopicity is highly dependent on the aerosol chemical composition. When there is a large mass fraction of inorganics and a small mass fraction of organic matter, f（RH） reaches a high value. The fraction of NO3^- was strongly correlated with the aerosol scattering coefficient at RH = 80%, which suggests that NO3^- played an important role in aerosol hygroscopic growth during the heavy pollution period.

Chemical Components, Variation, and Source Identification of PM1 during the Heavy Air Pollution Episodes in Beijing in December 2016

Air pollution is a current global concern. The heavy air pollution episodes（HPEs） in Beijing in December 2016 severely influenced visibility and public health. This study aims to survey the chemical compositions, sources, and formation processes of the HPEs. An aerodyne quadruple aerosol mass spectrometer（Q-AMS） was utilized to measure the non-refractory PM1（NR-PM1） mass concentration and size distributions of the main chemical components including organics, sulfate, nitrate, ammonium, and chloride in situ during 15–23 December 2016. The NR-PM1 mass concentration was found to increase from 6 to 188 μg m–3 within 5 days. During the most serious polluted episode, the PM1 mass concentration was about 2.6 times that during the first pollution stage and even 40 times that of the clean days. The formation rates of PM2.5 in the five pollution stages were 26, 22, 22, 32, and 67 μg m^（–3） h–1, respectively. Organics and nitrate occupied the largest proportion in the polluted episodes, whereas organics and sulfate dominated the submicron aerosol during the clean days. The size distribution of organics is always broader than those of other species, especially in the clean episodes. The peak sizes of the interested species grew gradually during different HPEs. Aqueous reaction might be important in forming sulfate and chloride, and nitrate was formed via oxidization and condensation processes. PMF（positive matrix factorization） analysis on AMS mass spectra was employed to separate the organics into different subtypes. Two types of secondary organic aerosol with different degrees of oxidation consisted of 43% of total organics. By contrast, primary organics from cooking, coal combustion, and traffic emissions comprised 57% of the organic aerosols during the HPEs.

Trace metals in atmospheric fine particles in one industrial urban city: Spatial variations, sources, and health implications

Trace metals in PM2.5 were measured at one industrial site and one urban site during September, 2010 in Ji＇nan, eastern China. Individual aerosol particles and PM2.5 samples were collected concurrently at both sites. Mass concentrations of eleven trace metals （i.e., Al, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Ba, and Pb） and one metalloid （i.e., As） were measured by inductively coupled plasma atomic emission spectroscopy （ICP-AES）. The result shows that mass concentrations of PM2.5 （130μg/m3） and trace metals （4.03 μg/m3） at the industrial site were 1.3 times and 1.7 times higher than those at the urban site, respectively, indicating that industrial activities nearby the city can emit trace metals into the surrounding atmosphere. Fe concentrations were the highest among all the measured trace metals at both sites, with concentrations of 1.04 ixg/m 3 at the urban site and 2.41 Itg/m3 at the industrial site, respectively. In addition, Pb showed the highest enrichment factors at both sites, suggesting the emissions from anthropogenic activities existed around the city. Correlation coefficient analysis and principal component analysis revealed that Cu, Fe, Mn, Pb, and Zn were originated from vehicular traffic and industrial emissions at both sites; As, Cr, and part of Pb from coal-fired power plant; Ba and Ti from natural soil. Based on the transmission electron microscopy analysis, we found that most of the trace metals were internally mixed with secondary sulfate/organic particles. These internally mixed trace metals in the urban air may have different toxic abilities compared with externally mixed trace metals.

Comparison of Submicron Particles at a Rural and an Urban Site in the North China Plain during the December 2016 Heavy Pollution Episodes

An extensive field experiment for measurement of physical and chemical properties of aerosols was conducted at an urban site in the Chinese Academy of Meteorological Sciences（CAMS） in Beijing and at a rural site in Gucheng（GC）, Hebei Province in December 2016. This paper compares the number size distribution of submicron particle matter（PM1, diameter 〈 1 μm） between the two sites. The results show that the mean PM1 number concentration at GC was twice that at CAMS, and the mass concentration was three times the amount at CAMS. It is found that the accumulation mode（100–850 nm） particles constituted the largest fraction of PM1 at GC, which was significantly correlated with the local coal combustion, as confirmed by a significant relationship between the accumulation mode and the absorption coefficient of soot particles. The high PM1 concentration at GC prevented the occurrence of new particle formation（NPF） events, while eight such events were observed at CAMS. During the NPF events, the mass fraction of sulfate increased significantly, indicating that sulfate played an important role in NPF. The contribution of regional transport to PM1 mass concentration was approximately 50% at both sites, same as that of the local emission. However, during the red-alert period when emission control took place, the contribution of regional transport was notably higher.

Simulating Aerosol Size Distribution and Mass Concentration with Simultaneous Nucleation,Condensation/Coagulation, and Deposition with the GRAPES–CUACE

A coupled aerosol–cloud model is essential for investigating the formation of haze and fog and the interaction of aerosols with clouds and precipitation. One of the key tasks of such a model is to produce correct mass and number size distributions of aerosols. In this paper, a parameterization scheme for aerosol size distribution in initial emission,which took into account the measured mass and number size distributions of aerosols, was developed in the GRAPES–CUACE [Global/Regional Assimilation and Pr Ediction System–China Meteorological Administration（CMA） Unified Atmospheric Chemistry Environment model]—an online chemical weather forecast system that contains microphysical processes and emission, transport, and chemical conversion of sectional multi-component aerosols. In addition, the competitive mechanism between nucleation and condensation for secondary aerosol formation was improved, and the dry deposition was also modified to be in consistent with the real depositing length. Based on the above improvements, the GRAPES–CUACE simulations were verified against observational data during 1–31 January 2013, when a series of heavy regional haze–fog events occurred in eastern China. The results show that the aerosol number size distribution from the improved experiment was much closer to the observation, whereas in the old experiment the number concentration was higher in the nucleation mode and lower in the accumulation mode. Meanwhile, the errors in aerosol number size distribution as diagnosed by its sectional mass size distribution were also reduced. Moreover, simulations of organic carbon, sulfate, and other aerosol components were improved and the overestimation as well as underestimation of PM2.5 concentration in eastern China was significantly reduced,leading to increased correlation coefficient between simulated and observed PM2.5 by more than 70%. In the remote areas where bad simulation results were produced previously, the correlation coefficient grew from 0.35 to 0.61, and the mean mass concentration went up from 43% to 87.5% of the observed value. Thus, the simulation of particulate matters in these areas has been improved considerably.