Secondary aerosol formation in winter haze over the BeijingTianjin-Hebei Region,China

Severe haze pollution occurs frequently in the winter over the Beijing-Tianjin-Hebei(BTH)region(China),exerting profound impacts on air quality,visibility,and human health.The Chinese Government has taken strict mitigation actions since 2013 and has achieved a significant reduction in the annual mean PM2.5 concentration over this region.However,the level of secondary aerosols during heavy haze episodes showed little decrease during this period.During heavy haze episodes,the concentrations of secondary aerosol components,including sulfate,nitrate and secondary organics,in aerosol particles increase sharply,acting as the main contributors to aerosol pollution.To achieve effective control of particle pollution in the BTH region,the precise and complete secondary aerosol formation mechanisms have been investigated,and advances have been made about the mechanisms of gas phase reaction,nucleation and heterogeneous reactions in forming secondary aerosols.This paper reviews the research progress in aerosol chemistry during haze pollution episodes in the BTH region,lays out the challenges in haze formation studies,and provides implications and directions for future research.

Haze formation in China: Importance of secondary aerosol

Air pollution is the world＇s largest single environmental hazard that causes more than a few million premature deaths in 2012（World Health Organization,2014）,particularly in developing countries with rapid industrialization and urbanization.Rapid economic growth of China in the last three decades has resulted in serious air pollution problems on both local and regional scales.

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 4–5 hr simulation, which was estimated to represent more than 10 days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol（SOA） production was 426 ± 85 mg/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.

Size distribution of the secondary organic aerosol particles from the photooxidation of toluene

In a smog chamber, the photooxidation of toluene was initiated by hydroxyl radical （OH.） under different experimental conditions. The size distribution of secondary organic aerosol（SOA） particles from the above reaction was measured using aerodynamic particle sizer spectrometer. It was found from our experimental results that the number of SOA particles increased with increasing the concentration of toluene. As the reaction time prolonged, the sum of SOA particles was also increased. After a reaction time of 130 min, the concentration of secondary organic aerosol particles would be kept constant at 2300 particles/cm^3. Increasing illumination power of blacklamps could significantly induce a higher concentration of secondary organic aerosol particle. The density of SOA particles would also be increased with increasing concentration of CH30NO, however, it would be decreased as soon as the concentration of CH30NO was larger than 225.2 ppm. Nitrogen oxide with initial concentration higher than 30. 1 ppm was also found to have little effect on the formation of secondary organic aerosol.

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.

Using Hourly Measurements to Explore the Role of Secondary Inorganic Aerosol in PM_(2.5)during Haze and Fog in Hangzhou, China

This paper explores the role of the secondary inorganic aerosol （SIA） species ammonium,NH4＋,nitrate,NO3-,and sulfate,SO24-,during haze and fog events using hourly mass concentrations of PM2.5 measured at a suburban site in Hangzhou,China.A total of 546 samples were collected between 1 April and 8 May 2012.The samples were analyzed and classified as clear,haze or fog depending on visibility and relative humidity （RH）.The contribution of SIA species to PM2.5 mass increased to ～50％ during haze and fog.The mass contribution of nitrate to PM2.5 increased from 11％ during clear to 20％ during haze episodes.Nitrate mass exceeded sulfate mass during haze,while near equal concentrations were observed during fog episodes.The role of RH on the correlation between concentrations of SIA and visibility was examined,with optimal correlation at 60％-70％ RH.The total acidity during clear,haze and fog periods was 42.38,48.38 and 45.51 nmol m-3,respectively,indicating that sulfate,nitrate and chloride were not neutralized by ammonium during any period.The nitrate to sulfate molar ratio,as a function of the ammonium to sulfate molar ratio,indicated that nitrate formation during fog started at a higher ammonium to sulfate molar ratio compared to clear and haze periods.During haze and fog,the nitrate oxidation ratio increased by a factor of 1.6-1.7,while the sulfur oxidation ratio increased by a factor of 1.2-1.5,indicating that both gaseous NO2 and SO2 were involved in the reduced visibility.

Effect of illumination intensity and light application time on secondary organic aerosol formation from the photooxidation of α-pinene

Secondary organic aerosol （SOA） formation from hydroxyl radical （OH.） initiated photooxidation of α-pinene was investigated in a home-made smog chamber. The size distribution of SOA particles was measured using aerodynamic particle sizer spectrometer. The effects of illumination intensity and light application time on SOA formation for α-pinene were evaluated. Experimental results show that the concentration of SOA particles increased significantly with an increasing of illumination intensity, and the light application time, the concentration, and the size of SOA particles were also increased. In addition, the factors influencing the formation of SOA were discussed. In addition, this article compared the effect of α-pinene with that of toluene, and discussed the contribution of α-pinene to SOA formation.

Role of secondary aerosols in haze formation in summer in the Megacity Beijing

A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibility 〈 10 km and RH（relative humidity） 〈 90%. Four haze episodes, which accounted for ～ 60% of the time during the whole campaign, were characterized by increases of SNA（sulfate, nitrate, and ammonium） and SOA（secondary organic aerosol） concentrations. The average values with standard deviation of SO2-＋4, NO-3, NH4 and SOA were 49.8（± 31.6）, 31.4（±22.3）, 25.8（±16.6） and 8.9（±4.1） μg/m3, respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO2-4,NO-3, NH＋4, and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM10 during the non-haze days. The respective contributions of SNA species to PM10 rose to about27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM10 mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR（sulfur oxidation ratio） and NOR（nitrogen oxidation ratio） increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO2 to SO2-4and NO2 to NO-3, which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing.

Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation

Anthropogenic emissions alter biogenic secondary organic aerosol(SOA)formation from naturally emitted volatileorganic compounds(BVOCs).We review the major laboratory and field findings with regard to effects of anthropogenicpollutants(NO_(x),anthropogenic aerosols,SO_(2),NH_(3))on biogenic SOA formation.NO_(x) participate in BVOC oxidationthrough changing the radical chemistry and oxidation capacity,leading to a complex SOA composition and yield sensitivitytowards NO_(x) level for different or even specific hydrocarbon precursors.Anthropogenic aerosols act as an importantintermedium for gas-particle partitioning and particle-phase reactions,processes of which are influenced by the particlephase state,acidity,water content and thus associated with biogenic SOA mass accumulation.SO_(2)modifies biogenic SOAformation mainly through sulfuric acid formation and accompanies new particle formation and acid-catalyzedheterogeneous reactions.Some new SO_(2)-involved mechanisms for organosulfate formation have also been proposed.NH_(3)/amines,as the most prevalent base species in the atmosphere,influence biogenic SOA composition and modify theoptical properties of SOA.The response of SOA formation behavior to these anthropogenic pollutants varies amongdifferent BVOCs precursors.Investigations on anthropogenic-biogenic interactions in some areas of China that aresimultaneously influenced by anthropogenic and biogenic emissions are summarized.Based on this review,somerecommendations are made for a more accurate assessment of controllable biogenic SOA formation and its contribution tothe total SOA budget.This study also highlights the importance of controlling anthropogenic pollutant emissions witheffective pollutant mitigation policies to reduce regional and global biogenic SOA formation.

Atmospheric photochemistry and secondary aerosol formation of urban air in Lyon,France

Photochemical aging of volatile organic compounds(VOCs)in the atmosphere is an important source of secondary organic aerosol(SOA).To evaluate the formation potential of SOA at an urban site in Lyon(France),an outdoor experiment using a Potential Aerosol Mass(PAM)oxidation flow reactor(OFR)was conducted throughout entire days during JanuaryFebruary 2017.Diurnal variation of SOA formations and their correlation with OH radical exposure(OHexp),ambient pollutants(VOCs and particulate matters,PM),Relative Humidity(RH),and temperature were explored in this study.Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of(0.2-1.2)×10^12 molecule/(cm^3·sec),corresponding to several days to weeks of equivalent atmospheric photochemical aging.The results informed that urban air at Lyon has high potency to contribute to SOA,and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis.Maximum SOA formation(36μg/m^3)was obtained at OHexp of about 7.4×10^11 molecule/(cm^3·sec),equivalent to approximately 5 days of atmospheric oxidation.The correlation between SOA formation and ambient environment conditions(RH&temperature,VOCs and PM)was observed.It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.

Effect of NOx and SO2 on the photooxidation of methylglyoxal:Implications in secondary aerosol formation

Methylglyoxal(CH3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3)K,atmospheric pressure,(18±2)%relative humidity,and under different NOx and SO2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS)and the results showed that the addition of SO2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO2 and MG/OH/NOx/SO2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS)and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR)analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.

Chemical composition and size distribution of secondary organic aerosol formed from the photooxidation of isoprene

Photooxidation of isoprene leads to the formation of secondary organic aerosol （SOA）. In this study, the chemical composition of SOA formed from OH-initiated photooxidation of isoprene has been investigated with gas chromatography/mass spectrometry （GC/MS） and a home-made aerosol time-of-fiight mass spectrometer. Sampling particles generated in a home-made smog chamber. The size distribution of SOA particles was detected by a TSI 3321 aerodynamic particle size spectrometer in real time. Results showed that SOA created by isoprene photooxidation was predominantly in the form of fine particles, which have diameters less than 2.5 μm. The obtained mass spectra of individual particles show that products of the OH-initiated oxidation of isoprene contain methyl vinyl ketone, methacrolein, formaldehyde, and some other hydroxycarbonyls. The possible reaction mechanisms leading to these products were also discussed.

Effects of NO_(2) and SO_(2) on the secondary organic aerosol formation fromβ-pinene photooxidation

Elucidating the effects of anthropogenic pollutants on the photooxidation of biogenic volatile organic compounds is crucial to understanding the fundamental mechanisms of secondary organic aerosol(SOA)formation.Here,the impacts of NO_(2)and SO_(2)on SOA formation from the photooxidation of a representative monoterpene,β-pinene,were investigated by a number of laboratory studies.The results indicated NO_(2)enhanced the SOA mass concentrations and particle number concentrations under both low and highβ-pinene conditions.This could be rationalized that the increased O_(3)concentrations upon the NO_(x)photolysis was helpful for the generation of more amounts of O_(3)-oxidized products,which accelerated the SOA nucleation and growth.Combing with NO_(2),the promotion of the SOA yield by SO_(2)was mainly reflected in the increase of mass concentration,which might be due to the elimination of the newly formed particles by the initially formed particles.The observed low oxidation degree of SOA might be attributed to the fast growth of SOA,resulting in the uptake of less oxygenated gas-phase species onto the particle phase.The present findings have important implications for SOA formation affected by anthropogenic–biogenic interactions in the ambient atmosphere.

Elaborations of the influencing factors on the formation of secondary inorganic aerosols in a heavily polluted urban area of China

In this study,online water-soluble inorganic ions were detected to deduce the formation mechanism of secondary inorganic aerosol in Xianyang,China during wintertime.The dominant inorganic ions of sulfate(SO_(4)^(2-)),nitrate(NO_(3)^(-)),and ammonium(NH_(4)^(+))(the sum of those is abbreviated as SNA)accounted for 17%,21%,and 12% of PM_(2.5)mass,respectively.While the air quality deteriorated from excellent to poor grades,the precursor gas sulfur dioxide(SO_(2))of SO_(4)^(2-)increased and then decreased with a fluctuation,while nitrogen dioxide(NO_(2))and ammonia(NH_(3)),precursors of NO_(3)^(-)and NH_(4)^(+),and SNA show increasing trends.Meteorological factors including boundary layer height(BLH),temperature,and wind speed also show decline trends,except relative humidity(RH).Meanwhile,the secondary conversion ratio shows a remarkable increasing trend,indicating that there was a strong secondary transformation.From the perspective of chemical mechanisms,RH is positively correlated with sulfur oxidation ratios(SOR),nitrogen oxidation ratios(NOR),and ammonia conversion ratios,representing that the increase of humidity could promote the generation of SNA.Notably,SOR and NOR were also positively related to the ammonia.On the one hand,the low wind speed and BLH led to the accumulation of pollutants.On the other hand,the increases of RH and ammonia promoted more formations of SNA and PM_(2.5).The results advance our identification of the contributors to the haze episodes and assist to establish more efficient emission controls in Xianyang,in addition to other cities with similar emission and geographical characteristics.

Second organic aerosol formation from the ozonolysis of α-pinene in the presence of dry submicron ammonium sulfate aerosol

An indoor chamber facility is described for investigation of atmospheric aerosol chemistry. Two sets of α-pinene ozonolysis experiments were conducted in the presence of dry ammonium sulfate seed particle: ozone limited experiments and α-pinene limited experiments. The concentration of gas phase and particle phase species was monitored continuously by on-line instruments and recorded automatically by data sampling system. The evolution of size distribution was measured by a scanning mobility particle sizer ...

Review of the influencing factors of secondary organic aerosol formation and aging mechanism based on photochemical smog chamber simulation methods

The formation and aging mechanism of secondary organic aerosol(SOA)and its influencing factors have attracted increasing attention in recent years because of their effects on climate change,atmospheric quality and human health.However,there are still large errors between air quality model simulation results and field observations.The currently undetected components during the formation and aging of SOA due to the limitation of current monitoring techniques and the interactions among multiple SOA formation influencing factors might be the main reasons for the differences.In this paper,we present a detailed review of the complex dynamic physical and chemical processes and the corresponding influencing factors involved in SOA formation and aging.And all these results were mainly based the studies of photochemical smog chamber simulation.Although the properties of precursor volatile organic compounds(VOCs),oxidants(such as OH radicals),and atmospheric environmental factors(such as NOx,SO2,NH3,light intensity,temperature,humidity and seed aerosols)jointly influence the products and yield of SOA,the nucleation and vapor pressure of these products were found to be the most fundamental aspects when interpreting the dynamics of the SOA formation and aging process.The development of techniques for measuring intermediate species in SOA generation processes and the study of SOA generation and aging mechanism in complex systems should be important topics of future SOA research.

Competing esterification and oligomerization reactions of typical long-chain alcohols to secondary organic aerosol formation

Organosulfate (OSA) nanoparticles,as secondary organic aerosol (SOA) compositions,are ubiquitous in urban and rural environments.Hence,we systemically investigated the mechanisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calculations.The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH^(-)groups to form carbenium ions (CBs),which engage in the subsequent esterification or oligomerization reactions to form OSAs/organosulfites (OSIs) or dimers.The kinetic results reveal that dehydration to form CBs for BOL and DOL reaction systems is the rate-limiting step.Subsequently,about 18%of CBs occur via oligomerization to dimers,which are difficult to further oligomerize because all reactive sites are occupied.The rate constant of BOL reaction system is one order of magnitude larger than that of DOL reaction system,implying that relative short-chain alcohols are more prone to contribute OSAs/OSIs than long-chain alcohols.Our results reveal that typical long-chain alcohols contribute SOA formation via esterification rather than oligomerization because OSA/OSI produced by esterification engages in nanoparticle growth through enhancing hygroscopicity.

Photodegradation of xylene isomers:Kinetics,mechanism,secondary pollutant formation potential and health risk evaluation

Photodegradation technology has been widely applied in the purification of industrial aromatic hydrocarbons.However,whether this technology efficiently removes the pollutants to prevent secondary pollution and health risk is still unclear.Here,the photodegradation processes of three xylenes were compared under designed reaction atmospheres and light sources.Xe lamp showed poor photodegradation ability toward xylenes,no matter in N_(2) or N_(2)+O_(2)system,while much higher photodegradation performance of xylenes were obtained under ultraviolet(UV)and vacuum ultraviolet(VUV)irradiation,especially in N_(2)+O_(2)+VUV system,where 97.9%of m-xylene,99.0%of o-xylene or 87.5%of p-xylene with the initial concentration of 860 mg/m^(3) was removed within 240 min.The xylenes underwent three processes of photo-isomerization,photodecomposition and photo-oxidation to produce intermediates of aromatics,alkanes and carbonyls.Among them,the photo-isomerization products showed the highest concentration percentage(e.g.,≥50%in o-xylene system),confirming that photo-isomerization reaction was the dominated photodegradation process of xylenes.Moreover,these isomerized products not only contributed about 97%and91%to the formation potential of O3(OFP)and secondary organic aerosols(SOAFP),but also displayed obvious non-carcinogenic risk,although one of photodecomposition product—benzene showed the highest occupational exposure risk.Therefore,the secondary pollution and health risks of photodegradation products of xylenes were non-ignorable,although the OFP,SOAFP and health risks of the generated products reduced at least 4.5 times in comparison with that of the degraded xylenes.The findings are helpful for the appropriate application of this technology in the purification of industrial organic waste gas.

Intensified wintertime secondary inorganic aerosol formation during heavy haze pollution episodes(HPEs) in Beijing,China

Air pollution in China is complex,and the formation mechanism of chemical components in particulate matter is still unclear.This study selected three consecutive heavy haze pollution episodes(HPEs)during winter in Beijing for continuous field observation,including an episode with heavy air pollution under red alert.Clean days during the observation period were selected for comparison.The HPE characteristics of Beijing in winter were:under the influence of adverse meteorological conditions such as high relative humidity,temperature inversion and low wind speed;and strengthening of secondary transformation reactions,which further intensified the accumulation of secondary aerosols and other pollutants,promoting the explosive growth of PM_(2.5).PM_(2.5)/CO values,as indicators of the contribution of secondary transformation in PM_(2.5),were approximately 2 times higher in the HPEs than the average PM_(2.5)/CO during the clean period.The secondary inorganic aerosols(sulfate nitrate and ammonium salt)were significantly enhanced during the HPEs,and the conversion coefficients were remarkably improved.In addition,it is interesting to observe that the production of sulfate tended to exceed that of nitrate in the late stage of all three HPEs.The existence of aqueous phase reactions led to the explosive growth sulfur oxidation ratio(SOR)and rapid generation of sulfate under high relative humidity(RH>70%).

Characteristics of Chemical Speciation in PM_(1)in Six Representative Regions in China

A better knowledge of aerosol properties is of great significance for elucidating the complex mechanisms behind frequently occurring haze pollution events.In this study,we examine the temporal and spatial variations in both PM_(1)and its major chemical constituents using three-year field measurements that were collected in six representative regions in China between 2012 and 2014.Our results show that both PM_(1)and its chemical compositions varied significantly in space and time,with high PM_(1)loadings mainly observed in the winter.By comparing chemical constituents between clean and polluted episodes,we find that the elevated PM_(1)mass concentration during pollution events should be largely attributable to significant increases in organic matter(OM)and inorganic aerosols like sulfate,nitrate,and ammonium(SNA),indicative of the critical role of primary emissions and secondary aerosols in elevating PM_(1)pollution levels.The ratios of PM_(1)/PM2.5 are found to be generally high in Shanghai and Guangzhou,while relatively low ratios are seen in Xi’an and Chengdu,indicating anthropogenic emissions were more likely to accumulate in forms of finer particles.With respect to the relative importance of chemical components and meteorological factors quantified via statistical modeling practices,we find that primary emissions and secondary aerosols were the two leading factors contributing to PM_(1)variations,though meteorological factors also played important roles in regulating the dispersion of atmospheric PM.