Aerosol Spectra and New Particle Formation Observed in Various Seasons in Nanjing

The aerosol number spectrum and gas pollutants were measured and the new particle formation （NPF） events were discussed in Nanjing. The results showed that the size distributions of aerosol number concen- trations exhibited distinct seasonal variations, implying the relations of particle sizes and their sources and sinks. The number concentrations of particles in the nuclei mode （10-30 nm）, Aitken mode （30-100 nm）, accumulation mode （100 -1000 nm） and coarse mode （〉1μm） varied in the order of summer 〉 spring 〉 autumn, summer 〉 autumn 〉 spring, autumn 〉 summer 〉 spring, and spring 〉 autumn 〉summer, re- spectively. The diurnal variation of total aerosol number concentrations showed three peaks in all observed periods, which corresponded to two rush hours and the photochemistry period at noon. In general, the NPF in summer occurred under the conditions of east winds and dominant air masses originating from marine areas with high relative humidity （50%-70%） and strong solar radiations （400 -700 W m-2）. In spring, the NPF were generally accompanied by low relative humidity （14%-30%） and strong solar radiations （400-600 W m-2）. The new particle growth rates （GR） were higher in the summertime in the range of 10- 16 nm h-1. In spring, the GR were 6.8-8.3 nm h-1. Under polluted air conditions, NPF events were seldom captured in autumn in Nanjing. During NPF periods, positive correlations between 10- 30 nm particles and 03 were detected, particularly in spring, indicating that NPF can be attributed to photochemical reactions.

Analysis on Concentration and Source Rate of Precursor Vapors Participating in Particle Formation and Growth at Xinken in the Pearl River Delta of China

Concentration and source rate of precursor vapors participating in particle formation and subsequent growth were investigated during the Pearl River Delta intensive campaign （PRD2004, October 2004） in southeastern China. Four new particle formation event days and a typical non-event day were selected for our analysis. Atmospheric sulphuric acid, the important precursor vapor in nucleation and growth, were simulated with a pseudo steady-state model based on the measurements of SO2, NOx, 03, CO, non-methane hydrocarbon （NMHC） and ambient particle number concentrations as well as modeled photolysis frequencies obtained from measurements. The maximum midday sulphuric acid concentrations vary from 4.53 × 10^7 to 2.17 × 10^8 molecules cm^-3, the corresponding source rate via reaction of OH and SO2 range between 2.37 × 10^6 and 1.16 × 10^7 molecules cm^-3 s^-1. Nucleation mode growth rate was derived from size spectral evolution during the events to be 6.8-13.8 nm h^-1. Based on the growth rate, concentration of the vapors participating in subsequent growth were estimated to vary from 1.32 × 10^8 to 2.80 × 10^8 molecules cm^-3 with corresponding source rate between 7.26 × 10^6 and 1.64 × 10^7 molecules cm^-3 s^-1. Our results show the degree of pollution is larger in PRD. Sulphuric acid concentrations are fairly high and have a close correlation with new particle formation events. Budget analysis shows that sulphuric acid alone is not enough for required growth; other nonvolatile vapors are needed. However, sulphuric acid plays an important role in growth; the contribution of sulphuric acid to growth in PRD is 12.4%-65.2%.

Particle number size distributions and formation and growth rates of different new particle formation types of a megacity in China

To understand the contribution of new particle formation(NPF)events to ambient fine particle pollution,measurements of particle size distributions,trace gases and meteorological conditions,were conducted at a suburban site(NJU)from October to December 2016 and at an industrial site(NUIST)from September to November 2015 in Nanjing.According to the temporal evolution of the particle size distributions,three types NPF events were observed:typical NPF(Type A),moderate NPF events(Type B)and strong NPF(Type C)events.The favorable conditions for Type A events included low relative humidity,low concentration of pre-existing particles,and high solar radiation.The favorable conditions of Type B events were similar to Type A,except for a higher concentration of pre-existing particles.Type C events were more likely to happen with the higher relative humidity,lower solar radiation and continuous growth of pre-existing particle concentration.The formation rate of 3 nm(J3)was the lowest for Type A events and highest for Type C events.In contrast,the growth rates of 10 nm and 40 nm particles were the highest for Type A,and lowest for Type C.Results show that NPF events with only higher J3 would lead to the accumulation of nucleation mode particles.Sulfuric acid was important for the formation of particles but had little effect on the growth of particle size.

Significant effects of transport on nanoparticles during new particle formation events in the atmosphere of Beijing

The mechanisms of new particle formation(NPF)events that occurred under high aerosol loadings(“polluted”NPF)in the atmosphere have been unclear,which has inhibited the precision of particlepollution control.To deepen the understanding of how the“polluted”NPF events occur,a one-monthcomprehensive measurement was conducted in the atmosphere of Beijing during the summer of2016.The“clean”NPF events(frequency=22%)(condensation sink,CS<0.015 s^(-1))were found to becaused by local nucleation and growth.The“polluted”NPF events(frequency=28%)(CS>0.015 s^(-1))were influenced by both local nucleation-growth and regional transport,and the contributions from thetwo factors to 6e25 nm particle number concentration were 60%and 40%,respectively.This studyemphasized the importance of the transport for nanoparticles in relatively polluted atmospheres,and forthat the regional joint particle pollution control would be an essential policy.

Particle number size distribution and new particle formation:New characteristics during the special pollution control period in Beijing

New particle formation is a key process in shaping the size distribution of aerosols in the atmosphere.We present here the measurement results of number and size distribution of aerosol particles （10–10000 nm in diameter） obtained in the summer of 2008,at a suburban site in Beijing,China.We firstly reported the pollution level,particle number size distribution,diurnal variation of the particle number size distribution and then introduced the characteristics of the particle formation processes.The results showed that the number concentration of ultrafine particles was much lower than the values measured in other urban or suburban areas in previous studies.Sharp increases of ultrafine particle count were frequently observed at noon.An examination of the diurnal pattern suggested that the burst of ultrafine particles was mainly due to new particle formation promoted by photochemical processes.In addition,high relative humidity was a key factor driving the growth of the particles in the afternoon.During the 2-month observations,new particle formation from homogeneous nucleation was observed for 42.7% of the study period.The average growth rate of newly formed particles was 3.2 nm/hr,and varied from 1.2 to 8.0 nm/hr.The required concentration of condensable vapor was 4.4×10 7 cm-3,and its source rate was 1.2×10 6 cm-3 sec-1.Further calculation on the source rate of sulphuric acid vapor indicated that the average participation of sulphuric acid to particle growth rates was 28.7%.

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.

Particle number size distribution and new particle formation (NPF) in Lanzhou,Western China

Particle number size distribution from 10 to 10,000 nm was measured by a wide-range particle spectrometer （WPS-1000XP） at a downwind site north of downtown Lanzhou, western China, from 25 june to 19 July 2006. We first report the pollution level, diurnal variation of particle concentration in different size ranges and then introduce the characteristics of the particle formation processes, to show that the number concentration of ultrafine particles was lower than the values measured in other urban or suburban areas in previous studies, However, the fraction of ultrafine particles in total aerosol number concentration was found to be much higher. Furthermore, sharp increase of ultrafine particle concentration was frequently observed at noon. An examination of the diurnal pattern suggests that the burst of the ultrafine particles was mainly due to nucleation process. During the 25-day observation, new particle formation （NPF） from homogeneous nucleation was observed during 33% of the study period. The average growth rate of the newly formed particles was 4.4 nm/h, varying from 1.3 to 16,9 nm/h. The needed concentration of condensable vapor was 6.1 × 10^7 cm-3, and its source rate was 1.1× 10^6 cm-3 s 1. Further calculation on the source rate of sulphuric acid vapor indicated that the average participation of sulphuric acid to particle growth rate was 68.3%.

Characterization of particle number size distribution and new particle formation in Southern China

Knowledge of particle number size distribution（PND） and new particle formation（NPF）events in Southern China is essential for mitigation strategies related to submicron particles and their effects on regional air quality,haze,and human health.In this study,seven field measurement campaigns were conducted from December 2013 to May 2015 using a scanning mobility particle sizer（SMPS） at four sites in Southern China,including three urban sites and one background site.Particles were measured in the size range of15-515 nm,and the median particle number concentrations（PNCs） were found to vary in the range of 0.3× 10~4-2.2 × 10~4 cn^（-3） at the urban sites and were approximately 0.2 × 10~4 cm^（-3） at the background site.The peak diameters at the different sites varied largely from 22 to 102 nm.The PNCs in the Aitken mode（25-100 nm） at the urban sites were up to 10 times higher than they were at the background site,indicating large primary emissions from traffic at the urban sites.The diurnal variations of PNCs were significantly influenced by both rush hour traffic at the urban sites and NPF events.The frequencies of NPF events at the different sites were0%-30%,with the highest frequency occurring at an urban site during autumn.With higher SO_2 concentrations and higher ambient temperatures being necessary,NPF at the urban site was found to be more influenced by atmospheric oxidizing capability,while NPF at the background site was limited by the condensation sink.This study provides a unique dataset of particle number and size information in various environments in Southern China,which can help understand the sources,formation,and the climate forcing of aerosols in this quickly developing region,as well as help constrain and validate NPF modeling.

Exploring the impact of new particle formation events on PM_(2.5) pollution during winter in the Yangtze River Delta,China

New particle formation(NPF)events are an increasingly interesting topic in air quality and climate science.In this study,the particle number size distributions,and the frequency of NPF events over Hefei were investigated from November 2018 to February 2019.The proportions of the nucleation mode,Aitken mode,and accumulation mode were 24.59%,53.10%,and 22.30%,respectively,which indicates the presence of abundant ultrafine particles in Hefei.Forty-six NPF events occurred during the observation days,accounting for 41.82%of the entire observation period.Moreover,the favorable meteorological conditions,potential precursor gases,and PM_(2.5)range of the NPF events were analyzed.Compared to non-NPF days,the NPF events preferentially occurred on days with lower relative humidity,higher wind speeds,and higher temperatures.When the PM_(2.5) was 15–20,70–80,and105–115μg/m^(3),the frequency of the NPF events was higher.Nucleation mode particles were positively related to atmospheric oxidation indicated by ozone when PM_(2.5) ranged from 15 to 20μg/m^(3),and related to gaseous precursors like SO_(2) and NO_(2) when PM_(2.5)was located at 70-80 and 105–115μg/m^(3).On pollution days,NPF events did not directly contribute to the increase in the PM_(2.5) in the daytime,however,NPF events would occur during the night and the growth of particulate matter contributes to the nighttime PM_(2.5) contents.This could lead to pollution that lasted into the next day.These findings are significant to the improvement of our understanding of the effects of aerosols on air quality.

STUDY ON THE FORMATION MECHANISM OF MONODISPERSE PARTICLES IN THE EMULSIFIER-FREE EMULSION POLYMEAIZATION OF METHYL METHACRYLATE AND BUTYL ACRYLATE

The formation mechanism of monodisperse polymer latex particles in the emulsifier-free emulsion polymerizationof methyl methacrylate and butyl acrylate with potassium persulfate as initiator was investigated. A multi-step formationmechanism for the monodisperse polymer particles was proposed. The nucleation mechanism is considered to be thecoagulation of the precursor particles by homogeneous nucleation when the primary particles reach a critical size with highsurface charge density and sufficient stability. It had been proved by a special experiment that the early latex particles formedby the coagulation were stable. The primary particles grow by absorbing monomers and radicals in the polymerization systemand then become colloidally unstable again due to the understandable decrease of particle surface charge density, which leadsto the aggregation of the growing particles and the formation of larger latex pedicles therefrom. Aner the nucleation period,the preferential aggregation of the smaller particles in the propagation process leads to the change of the particles towards auniform size and narrower particle size distribution. The coexistence and competition of homogeneous nucleation,coagulation, propagation and aggregation result in the increase of the polydispersity index (U = D_(43)/D_(10)) in the first Stage,then its decrease in the later stage because of the competition of propagation and aggregation, and the gradual formation ofthe monodisperse particles.

Formation of Ultrafine Metal Particles and Metal Oxide Precursor on Anodized Al by Electrolysis Deposition

Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.

Diurnal variation of number concentration and size distribution of ultrafine particles in the urban atmosphere of Beijing in winter

Number concentration and distribution of airborne particles in the size range 5.6 to 560 nm diameter were measured in Beijing for a 15-d period in winter 2005. Dally average number concentrations of nucleation mode （5.6-20 um）, Aitken mode （20-100 um）, and accumulation mode （100-560 um） particles, and total particles were 17500, 32000, 4000, and 53500 cm^-3, respectively. Average particle size distribution was monomodal with a mode diameter of about 40 um at night and bimodal with mode diameters of about 10 and about 40 um during the daytime. New particle formation events, which were connected to diurnal variation of nucleation mode particles, were observed in more than half of the observation days. The events often started around 10：00-11：00 Chinese Standard Time （CST） and ended up after 3-4 h. Concentrations of Aitken and accumulation mode particles increased from midnight and reached their maxima at about 10：00 CST, and then decreased and became the lowest in the afternoon. Analysis of diurnal cycles in traffic volume and meteorological parameters revealed that the accumulation of the particles in Aitken and accumulation modes in the morning was influenced by formation of an inversion and increase in vehicle emission, and dispersion of such particles in the afternoon was associated with more effective vertical mixing and higher wind speed.

PARTICLE MORPHOLOGY OF POLY(VINYL CHLORIDE)RESIN PREPARED BY SUSPENDED EMULSION POLYMERIZATION

Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.

Compilation of reaction kinetics parameters determined in the Key Development Project for Air Pollution Formation Mechanism and Control Technologies in China

A compilation of new advances made in the research?eld of laboratory reaction kinetics in China’s Key Development Project for Air Pollution Formation Mechanism and Control Technologies was presented.These advances are grouped into six broad,interrelated categories,including volatile organic compound(VOC)oxidation,secondary organic aerosol(SOA)formation,new particle formation(NPF)and gas-particle partitioning,ozone chemistry,model parameters,and secondary inorganic aerosol(SIA)formation,highlighting the laboratory work done by Chinese researchers.For smog chamber applications,the current knowledge gained from laboratory studies is reviewed,with emphasis on summarizing the oxidation mechanisms of long-chain alkanes,aromatics,alkenes,aldehydes/ketones in the atmosphere,SOA formation from anthropogenic emission sources,and oxidation of aromatics,isoprene,and limonene,as well as SIA formation.For?ow tube applications,atmospheric oxidation mechanisms of toluene and methacrolein,SOA formation from limonene oxidation by ozone,gas-particle partitioning of peroxides,and sulfuric acid-water(H2SO4-H2O)binary nucleation,methanesulfonic acid-water(MSA-H2O)binary nucleation,and sulfuric acid-ammonia-water(H2SO4-NH3-H2O)ternary nucleation are discussed.

Formation mechanism of typical aromatic sulfuric anhydrides and their potential role in atmospheric nucleation process

Sulfuric anhydrides,generated from the cycloaddition reaction of SO3with carboxylic acids,have been revealed to be potential participants in the nucleation process of new particle formation(NPF).Hence the reaction mechanisms of typical aromatic acids(benzoic acid(BA),phenylacetic acid(PAA),phthalic acid(PA),isophthalic acid(mPA),and terephthalic acid(PTA))with SO3to generate the corresponding aromatic sulfuric anhydrides were investigated by density functional theory calculations at the level of M06-2X/6-311++G(3df,3pd).As a result,these reactions were found to be feasible in the gas phase with barriers of 0.34,0.30,0.18,0.08 and 0.12 kcal/mol to generate corresponding aromatic sulfuric anhydrides,respectively.The thermodynamic stabilities of clusters containing aromatic sulfuric anhydrides and atmospheric nucleation precursors(sulfuric acid,ammonia and dimethylamine)were further analyzed to identify the potential role of aromatic sulfuric anhydrides in NPF.As the thermodynamic stability of a cluster depends on both the number and strength of hydrogen bonds,the greater stability of the interactions between atmospheric nucleation precursors and aromatic sulfuric anhydrides than with aromatic acids make aromatic sulfuric anhydrides potential participators in the nucleation process of NPF.Moreover,compared with BA,the addition of a-CH_(2)-functional group in PAA has little influence on the reaction barrier with SO3but an inhibitive effect on the thermodynamic stability of clusters.The position of the two-COOH functional groups in PA,m PA and PTA does not have a consistent impact on the reaction barrier with SO3or the thermodynamic stability.

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 350 nm 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 1.55 g/cm3, on average. The effective particle density distributions were dominated by a mode peaked at around 1.5 g/cm3 for 50 to 350 nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6 g/cm3 for 150, 240, and 350 nm 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.

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.

DROPLETS AND PARTICLES IN SPRAYS: TAILORING PARTICLE PROPERTIES WITHIN SPRAY PROCESSES

Particle generation via atomization and spray processes is a widely applied method for powder production. By means of atomization processes, the relevant particle properties may be tailored to the powder user's need in a wide range. Understanding and control of the main subprocesses of atomization is a key feature for choosing a suitable type of spray process and operation conditions. Tailoring particle properties and extending the applications of particle production beyond the current limits is also possible in this way. This contribution highlights some features of spray processes for powder production, namely the gas- and fluid-dynamic processes involved, the materials-related subprocesses, and the formation of the multiphase flow in the spray. As an example, the production of fibre- or sphere-shaped particles from melt atomization is discussed.

Smog chamber study on the evolution of fume from residential coal combustion

Domestic coal stoves are widely used in countryside and greenbelt residents in China for heating and cooking,and emit considerable pollutants to the atmosphere because of no treatment of their exhaust,which can result in deteriorating local air quality.In this study,a dynamic smog chamber was used to investigate the real-time emissions of gaseous and particulate pollutants during the combustion process and a static smog chamber was used to investigate the fume evolution under simulate light irradiation.The real-time emissions revealed that the total hydrocarbon （THC） and CO increased sharply after ignition,and then quickly decreased,indicating volatilization of hydrocarbons with low molecular weight and incomplete combustion at the beginning stage of combustion made great contribution to these pollutants.There was evident shoulder peak around 10min combustion for both THC and CO,revealing the emissions from vitrinite combustion.Additionally,another broad emission peak of CO after 30min was also observed,which was ascribed to the incomplete combustion of the inertinite.Compared with THC and CO,there was only one emission peak for NOx,SO 2 and particular matters at the beginning stage of combustion.The fume evolution with static chamber simulation indicated that evident consumption of SO 2 and NOx as well as new particle formation were observed.The consumption rates for SO 2 and NOx were about 3.44% hr-1 and 3.68% hr-1,the new particle formation of nuclei particles grew at a rate of 16.03 nm/hr during the first reaction hour,and the increase of the diameter of accumulation mode particles was evident.The addition of isoprene to the diluted mixture of the fume could promote O 3 and secondary particle formation.

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

Due to profound impact on climate and human health,air quality has attracted attention from all levels of the civil society.The key step in the provision of required tools for the society to tackle the complex air quality problem is to characterize it in a comprehensive manner with a long-term perspective.Here,we describe a continuous and comprehensive observation station and its accompanying state-ofthe-art instrumentation that was established to investigate the complex urban atmospheric environment in a rapidly developing Chinese Megacity.The station,located in downtown Beijing,aims to study air quality by identifying the major atmospheric pollutants and key processes determining their formation and loss mechanisms.A few hundreds of parameters are continuously measured with the state-of-the-art instruments,including trace gas concentrations,aerosol particle size distributions,and mass concentrations,covering aerosol particle chemical composition from molecules to micrometer-sized aerosol particles.This produced long-term,comprehensive big data with around 1�10^(11)bytes per year.In this paper,we provide an overview on the facilities of the station,the instrumentation used,the workflow of continuous observations and examples of results from 2018 to 2019 and a basis for establishing a modern long-term,comprehensive atmospheric urban observation station in other megacities.