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.

Secondary organic aerosol formation from straw burning using an oxidation flow reactor

Herein,we use an oxidation flow reactor,Gothenburg:Potential Aerosol Mass(Go:PAM)reactor,to investigate the secondary organic aerosol(SOA)formation from wheat straw burning.Biomass burning emissions are exposed to high concentrations of hydroxyl radicals(OH)to simulate processes equivalent to atmospheric oxidation of 0-2.55 days.Primary volatile organic compounds(VOCs)were investigated,and particles were measured before and after the Go:PAM reactor.The influence of water content(i.e.5%and 11%)in wheat straw was also explored.Two burning stages,the flaming stage,and non-flaming stages,were identified.Primary particle emission factors(EFs)at a water content of 11%(~3.89 g/kg-fuel)are significantly higher than those at a water content of 5%(~2.26 g/kg-fuel)during the flaming stage.However,the water content showed no significant influence at the non-flaming stage.EFs of aromatics at a non-flaming stage(321.8±46.2 mg/kg-fuel)are larger than that at a flaming stage(130.9±37.1 mg/kg-fuel).The OA enhancement ratios increased with the increase in OH exposure at first and decreased with the additional increment of OH exposure.The maximum OA enhancement ratio is~12 during the non-flaming stages,which is much higher than~1.7 during the flaming stages.The mass spectrum of the primary wheat burning organic aerosols closely resembles that of resolved biomass burning organic aerosols(BBOA)based on measurements in ambient air.Our results show that large gap(0%-90%)still remains to estimate biomass burning SOA if only the oxidation of VOCs were included.

Assessing the influence of environmental conditions on secondary organic aerosol formation from a typical biomass burning compound

The atmospheric chemistry in complex air pollution remains poorly understood.In order to probe how environmental conditions can impact the secondary organic aerosol(SOA)formation from biomass burning emissions,we investigated the photooxidation of 2,5-dimethylfuran(DMF)under different environmental conditions in a smog chamber.It was found that SO_(2)could promote the formation of SOA and increase the amounts of inorganic salts produced during the photooxidation.The formation rate of SOA and the corresponding SOA mass concentration increased gradually with the increasing DMF/OH ratio.The addition of(NH_(4))_(2)SO_(4)seed aerosol accelerated the SOA formation rate and significantly shortened the time for the reaction to reach equilibrium.Additionally,a relatively high illumination intensity promoted the formation of OH radicals and,correspondingly,enhanced the photooxidation of DMF.However,the enhancement of light intensity accelerated the aging of SOA,which led to a gradual decrease of the SOA mass concentration.This work shows that by having varying influence on atmospheric chemical reactions,the same environmental factor can affect SOA formation in different ways.The present study is helpful for us to better understand atmospheric complex pollution.

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.

Ozone and secondary organic aerosol formation potential from anthropogenic volatile organic compounds emissions in China

Volatile organic compounds （VOCs） are major precursors for ozone and secondary organic aerosol （SOA）, both of which greatly harm human health and significantly affect the Earth＇s climate. We simultaneously estimated ozone and SOA formation from anthropogenic VOCs emissions in China by employing photochemical ozone creation potential （POCP） values and SOA yields. We gave special attention to large molecular species and adopted the SOA yield curves from latest smog chamber experiments. The estimation shows that alkylbenzenes are greatest contributors to both ozone and SOA formation （36.0% and 51.6%, respectively）, while toluene and xylenes are largest contributing individual VOCs. Industry solvent use, industry process and domestic combustion are three sectors with the largest contributions to both ozone （24.7%, 23.0% and 17.8%, respectively） and SOA （22.9%, 34.6% and 19.6%, respectively） formation. In terms of the formation potential per unit VOCs emission, ozone is sensitive to open biomass burning, transportation, and domestic solvent use, and SOA is sensitive to industry process, domestic solvent use, and domestic combustion. Biomass stoves, paint application in industrial protection and buildings, adhesives application are key individual sources to ozone and SOA formation, whether measured by total contribution or contribution per unit VOCs emission. The results imply that current VOCs control policies should be extended to cover most important industrial sources, and the control measures for biomass stoves should be tightened. Finally, discrepant VOCs control policies should be implemented in different regions based on their ozone/aerosol concentration levels and dominant emission sources for ozone and SOA formation potential.

MEASUREMENTS OF PARTICLE NUMBER SIZE DISTRIBUTIONS AND NEW PARTICLE FORMATION EVENTS DURING WINTER IN THE PEARL RIVER DELTA REGION,CHINA

Particle number size distribution(PNSD) between 10 nm and 20 μm were measured in the Pearl River Delta(PRD) region in winter 2011.The average particle number concentration of the nucleation mode(10-20 nm),Aitken mode(20-100 nm),accumulation mode(100 nm-1μm) and coarse mode(1-20 μm) particles were 1 552,7 470,4 012,and 19 cm-3,respectively.The volume concentration of accumulation mode particles with peak at 300 nm accounted for over 70% of the total volume concentration.Diurnal variations and dependencies on meteorological parameters of PNSD were investigated.The diurnal variation of nucleation mode particles was mainly influenced by new particle formation events,while the diurnal variation of Aitken mode particles correlated to the traffic emission and the growth process of nucleation mode particles.When the PRD region was controlled by a cold high pressure,conditions of low relative humidity,high wind speed and strong radiation are favorable for the occurrence of new particle formation(NPF) events.The frequency of occurrence of NPF events was 21.3% during the whole measurement period.Parameters describing NPF events,including growth rate(GR) and source rate of condensable vapor(Q),were slightly larger than those in previous literature.This suggests that intense photochemical and biological activities may be the source of condensable vapor for particle growth,even during winter in the PRD.

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.

Environmental impact and health risk assessment of volatile organic compound emissions during different seasons in Beijing

Volatile organic compounds(VOCs)are major contributors to air pollution.Based on the emission characteristics of 99 VOCs that daily measured at 10 am in winter from 15 December 2015 to 17 January 2016 and in summer from 21 July to 25 August 2016 in Beijing,the environmental impact and health risk of VOC were assessed.In the winter polluted days,the secondary organic aerosol formation potential(SOAP)of VOC(199.70±15.05 mg/m^3)was significantly higher than that on other days.And aromatics were the primary contributor(98.03%)to the SOAP during the observation period.Additionally,the result of the ozone formation potential(OFP)showed that ethylene contributed the most to OFP in winter(26.00%and 27.64%on the normal and polluted days).In summer,however,acetaldehyde was the primary contributor to OFP(22.00%and 21.61%on the normal and polluted days).Simultaneously,study showed that hazard ratios and lifetime cancer risk values of acrolein,chloroform,benzene,1,2-dichloroethane,acetaldehyde and 1,3-butadiene exceeded the thresholds established by USEPA,thereby presenting a health risk to the residents.Besides,the ratio of toluene-to-benzene indicated that vehicle exhausts were the main source of VOC pollution in Beijing.The ratio of m-/p-xylene-toethylbenzene demonstrated that there were more prominent atmospheric photochemical reactions in summer than that in winter.Finally,according to the potential source contribution function(PSCF)results,compared with local pollution sources,the spread of pollution from long-distance VOCs had a greater impact on Beijing.