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 ...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.展开更多
Fine particle of organic aerosol (OA), mostly arising from pollution, are abundant in Beijing. To achieve a better un- derstanding of the difference in OA in summer and autumn, a high-resolution time-of-flight aeros...Fine particle of organic aerosol (OA), mostly arising from pollution, are abundant in Beijing. To achieve a better un- derstanding of the difference in OA in summer and autumn, a high-resolution time-of-flight aerosol mass spectrometer (HR- ToF-AMS, Aerodyne Research Inc., USA) was deployed in urban Beijing in August and October 2012. The mean OA mass concentration in autumn was 30 4-30 μg m-3, which was higher than in summer (13 4-6.9 μg m-3). The elemental anal- ysis found that OA was more aged in summer (oxygen-to-carbon (O/C) ratios were 0.41 and 0.32 for summer and autumn, respectively). Positive matrix factorization (PMF) analysis identified three and five components in summer and autumn, re- spectively. In summer, an oxygenated OA (OOA), a cooking-emission-related OA (COA), and a hydrocarbon-like OA (HOA) were indentified. Meanwhile, the OOA was separated into LV-OOA (low-volatility OOA) and SV-OOA (semi-volatile OOA); and in autumn, a nitrogen-containing OA (NOA) was also found. The SOA (secondary OA) was always the most important OA component, accounting for 55% of the OA in the two seasons. Back trajectory clustering analysis found that the origin of the air masses was more complex in summer. Southerly air masses in both seasons were associated with the highest OA loading, while northerly air masses were associated with the lowest OA loading. A preliminary study of OA components, especially the POA (primary OA), in different periods found that the HOA and COA all decreased during the National Day holiday period, and HOA decreased at weekends compared with weekdays.展开更多
The concentration of PM_(2.5)has considerably reduced in recent years,but remains relatively high in China.In particular,the increasing contribution of organic compounds to PM_(2.5)generates popular pressure for furth...The concentration of PM_(2.5)has considerably reduced in recent years,but remains relatively high in China.In particular,the increasing contribution of organic compounds to PM_(2.5)generates popular pressure for further reductions,resulting in an urgent need to study organic aerosol(OA).To investigate the molecular composition and source contribution of OA in the rural area of the Guanzhong Plain,Northwest China,PM_(2.5)samples were collected during 3–23 August 2016 and 5–20 January 2017 and studied for more than 100 organic tracer compounds.The mean concentration of total measured organic compounds is 662±296 ng/m^(3)in summer and 3258±1925 ng/m^(3)in winter.Levoglucosan is the most abundant single compound found throughout the sampling period,which is a crucial tracer for biomass burning emissions,preliminary suggesting that biomass burning is an essential source of OA.In summer,organic compounds such as lipid compounds,sugar compounds,and polycyclic aromatic hydrocarbons(PAHs),more come from higher plants,wood burning,vehicle exhausts,plastic waste,and other direct emission sources.Oxygenated PAHs(OPAHs),nitrophenols,and phthalic acids more come from the atmosphere through the oxidation reaction of aromatic precursors,especially photochemical oxidation.However,in winter,most of the increases in concentrations of organic compounds are attributed to biomass burning.The analysis of a haze event(14–19 January 2017)during the winter sampling period shows that the increases in the concentration of organic compounds are unaccompanied by strong secondary formation under lower relative humidity(49.1%±13.5%).The main reason for the growth of OA in this haze event is the accumulation of primary OA(POA).The source apportionment by the positive matrix factorization(PMF)model shows that biomass burning(37.1%)is the primary source of OA in the rural regions of the Guanzhong Plain,especially in winter(40.6%).The contribution of secondary formation decreases from 26.0%in summer to 16.9%in winter,and the contribution of fossil fuel emissions is comparable across both seasons.展开更多
To better understand the seasonal characteristics of urban organic aerosol(OA)in the North China Plain(NCP),PM2.5 samples in the urban atmosphere of Liaocheng were collected and analyzed.The molecular distribution of ...To better understand the seasonal characteristics of urban organic aerosol(OA)in the North China Plain(NCP),PM2.5 samples in the urban atmosphere of Liaocheng were collected and analyzed.The molecular distribution of the organic markers in the urban atmosphere of Liaocheng reveals that n-alkanes(39.3%)was the most abundant species all year round,followed by saccharides(28.2%),phthalic acids(Ph,20.8%),biogenic secondary organic aerosol(BSOA)tracers(9.4%),and polycyclic aromatic hydrocarbon(PAHs,2.3%).PM2.5,organic carbon(OC),elemental carbon(EC),and primary organic markers exhibit the highest concentrations in winter,due largely to the increased biomass burning and coal combustion for house heating in local and surrounding regions.However,the concentration and relative abundance of BSOA are significantly higher in summer than other seasons,induced by the more favorable meteoro-logical conditions that would promote the emissions of biogenic volatile organic compounds(BVOCs)and the secondary production of BSOA.The ratios of OC/EC and 3-methyl-1,2,3-butanetricarboxylic acid to cis-pinic acid plus cis-pinonic acid(MBTCA/(PA+PNA)are higher in the warm seasons than those in the cold seasons,indicating that the oxidation of OA is sensitive to air temperature.Compared to 2017,the concentration level of PAHs during wintertime decreased by 40.8%,confirming that the stringent regulation of coal burning is effective.The highest concentration of high molecular weight(HMW)n-alkanes and three anhydrosugars in winter,and the close correlation of levoglucosan with HMW n-al-kanes suggests that the impact of biomass burning was more significant in winter.The same seasonal characteristic of the ratios of high-/low-NO_(x) products with NO_(x) and the strong correlation of high-/low-NO_(x) products with levoglucosan indicate that the formation of isoprene SOA(SOA1)tracers was signif-icantly influenced by anthropogenic emissions.The molecular compositions,the distributions of fire spots,backward trajectories of air masses,and correlation analysis suggest that air pollution events in spring were primarily resulted from biomass burning and secondary oxidation,while pollution events in winter were largely driven by the increased combustion sources,and promoted aqueous secondary formation.Our results suggest that the reduction of biomass and coal combustion should be taken into account to improve the urban air quality in the NCP.展开更多
Size-resolved biogenic secondary organic aerosols (BSOA) derived from isoprene and monoterpene photooxidation in Qinghai Lake, Tibetan Plateau (a continental background site) and five cities of China were measured...Size-resolved biogenic secondary organic aerosols (BSOA) derived from isoprene and monoterpene photooxidation in Qinghai Lake, Tibetan Plateau (a continental background site) and five cities of China were measured using gas chromatography/mass spectrometry (GC/MS). Concentrations of the determined BSOA are higher in the cities than in the background and are also higher in summer than in winter. Moreover, strong positive correlations (R^2 = 0.44-0.90) between BSOA and sulfate were found at the six sites, suggesting that anthropogenic pollution (i.e., sulfate) could enhance SOA formation, because sulfate provides a surface favorable for acid-catalyzed formation of BSOA. Size distribution measurements showed that most of the determined SOA tracers are enriched in the fine mode (〈3.3 μm) except for cis-pinic and cis-pinonic acids, both presented a comparable mass in the fine and coarse (〉3.3 μm) modes, respectively. Mass ratio of oxidation products derived from isoprene to those from monoterpene in the five urban regions during summer are much less than those in Qinghai Lake region. In addition, in the five urban regions relative abundances of monoterpene oxidation products to SOA are much higher than those of isoprene. Such phenomena suggest that BSOA derived from monoterpenes are more abundant than those from isoprene in Chinese urban areas.展开更多
Primary and secondary organic aerosols in PM_(2.5)were investigated over a one-year campaign at Zouk Mikael and Fiaa,Lebanon.The n-alkanes concentrations were quite similar at both sites(26-29 ng/m^(3))and mainly expl...Primary and secondary organic aerosols in PM_(2.5)were investigated over a one-year campaign at Zouk Mikael and Fiaa,Lebanon.The n-alkanes concentrations were quite similar at both sites(26-29 ng/m^(3))and mainly explained by anthropogenic emissions rather than natural ones.The concentrations of total Polycyclic Aromatic Hydrocarbons(PAHs)were nearly three times higher at Zouk Mikael(2.56 ng/m^(3))compared to Fiaa(0.95 ng/m^(3)),especially for indeno[1,2,3-c,d]pyrene linked to the presence of the power plant.A characteristic indeno[1,2,3-c,d]pyrene/(indeno[1,2,3-c,d]pyrene+benzo[g,h,i]perylene)ratio in the range0.8-1.0 was determined for heavy fuel oil combustion from the power plant.Fatty acids and hopanes were also investigated and were assigned to cooking activities and vehicular emissions respectively.Phthalates were identified for the first time in Lebanon with high concentrations at Zouk and Fiaa(106.88 and 97.68 ng/m^(3) respectively).Moreover,the biogenic secondary aerosols revealed higher concentrations in summer.The total terpene concentration varied between 131 ng/m^(3) at Zouk Mikael in winter to 469 ng/m3 at Fiaa in summer.Additionnally,the concentrations of the dicarboxylic acids especially for adipic and phthalic acids were more influenced by anthropogenic sources.The analysis of molecular markers and diagnostic ratios indicated that the sites were strongly affected by anthropogenic sources such as waste open burning,diesel private generators,cooking activities,road transport,power plant,and industrial emissions.Moreover,results showed different pattern during winter and summer seasons.Whereas,higher concentrations of biogenic markers were clearly encountered during the summer period.展开更多
The International Centre for Theoretical Physics(ICTP,Italy) Regional Climate Model version 3.0(RegCM3) is used to simulate spatio-temporal distribution characteristics and radiative forcing(RF) of organic carbon(OC) ...The International Centre for Theoretical Physics(ICTP,Italy) Regional Climate Model version 3.0(RegCM3) is used to simulate spatio-temporal distribution characteristics and radiative forcing(RF) of organic carbon(OC) aerosols in and around China.The preliminary simulation results show that OC aerosols are mostly concentrated in the area to the south of Yellow River and east of Tibetan Plateau.There is a decreasing trend of column burden of OC aerosols from south to north in China.The maximum value of column burden of OC aerosols is above 3 mg/m2 and located in the central and southern China,southeastern Tibet,and southwestern China's Yunnan,Guizhou,Sichuan provinces.The simulation on the seasonal variation shows that the maximum value of column burden of OC aerosols appears in winter and the secondary value is in spring and the minimum in summer.The RF of OC aerosols which varies seasonally is negative at the top of the atmosphere(TOA) and surface.The spatio-temporal characteristics of the RF of OC aerosols are basically consistent with that of IPCC,implying the high accuracy of the parameterization scheme for OC aerosols in RegCM3.展开更多
The North China Plain(NCP)is a region that experiences serious aerosol pollution.A number of studies have focused on aerosol pollution in urban areas in the NCP region;however,research on characterizing aerosols in ru...The North China Plain(NCP)is a region that experiences serious aerosol pollution.A number of studies have focused on aerosol pollution in urban areas in the NCP region;however,research on characterizing aerosols in rural NCP areas is comparatively limited.In this study,we deployed a TD-HR-AMS(thermodenuder high-resolution aerosol mass spectrometer)system at a rural site in the NCP region in summer 2013 to characterize the chemical compositions and volatility of submicron aerosols(PM_(1)).The average PM_(1)mass concentration was 51.2±48.0μg m^(−3) and organic aerosol(OA)contributed most(35.4%)to PM_(1).Positive matrix factorization(PMF)analysis of OA measurements identified four OA factors,including hydrocarbon-like OA(HOA,accounting for 18.4%),biomass burning OA(BBOA,29.4%),lessoxidized oxygenated OA(LO-OOA,30.8%)and more-oxidized oxygenated OA(MO-OOA,21.4%).The volatility sequence of the OA factors was HOA>BBOA>LO-OOA>MO-OOA,consistent with their oxygen-to-carbon(O:C)ratios.Additionally,the mean concentration of organonitrates(ON)was 1.48−3.39μg m−3,contributing 8.1%-19%of OA based on cross validation of two estimation methods with the high-resolution time-of-flight aerosol mass spectrometer(HRToF-AMS)measurement.Correlation analysis shows that ON were more correlated with BBOA and black carbon emitted from biomass burning but poorly correlated with LO-OOA.Also,volatility analysis for ON further confirmed that particulate ON formation might be closely associated with primary emissions in rural NCP areas.展开更多
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...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.展开更多
Aerosols represent an important source of terrestrial organic carbon(OC)from the East Asian continent to the China marginal seas,thus their provenance and transport play important roles in the global carbon cycle.Fift...Aerosols represent an important source of terrestrial organic carbon(OC)from the East Asian continent to the China marginal seas,thus their provenance and transport play important roles in the global carbon cycle.Fifty samples of total suspended particle were collected seasonally from the nearshore Huaniao Island(HNI)in East China Sea(ECS)from April 2018 to January 2019;and they were analyzed for total organic carbon(TOC)content and stable carbon isotope(δ^(13)C),as well as terrestrial bio-markers including n-alkanes(C_(20)-C_(33)),n-alkanols(C_(20)-C32)and n-fatty acids(n-FAs,C_(20)-C30),to distinguish the seasonal variabili-ties of terrestrial OC sources and reveal the influence of the long-range air mass transport on these sources.The TOC-δ^(13)C values(range from−27.3‰to−24.3‰)and molecular distributions of terrestrial biomarkers both suggested that terrestrial OC contribu-tions to aerosols had significant seasonal variations.The source indices of terrestrial biomarkers(e.g.,Fossil%=82.8%for n-alkanes)revealed that the fossil fuel OC contributions,including coal burning and vehicular emission,were higher in winter,mainly because of the long-range air mass transport from the north of the East Asian continent.The terrestrial plant OC contributions were higher in summer(e.g.,Wax%=32.4%for n-alkanes),likely due to local vegetation sources from HNI and East Asian continental air masses.Cluster analysis of air mass backward-trajectories clearly showed that transport pathway plays an important role in determining the organic constituents of aerosols in China marginal seas.A comparison of these terrestrial OC contributions from different air mass origins suggested that fossil fuel OC showed less variations among various air mass origins from northern China in winter,while terrestrial plant OC sources from northern and southern China in summer contributed more than that from the air masses transported through the ECS.These results provided a basis for future quantification of terrestrial OC from different origins in marine aerosols,by combining biomarker index and carbon isotopes.展开更多
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 re...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.展开更多
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 a...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.展开更多
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 anthro...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.展开更多
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 limi...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 ...展开更多
As Volatile Organic Compounds(VOCs)are one of the precursors of ozone,their distribution and variable concentrations are highly related to local ozone pollution control.In this study,we obtained vertical profiles of V...As Volatile Organic Compounds(VOCs)are one of the precursors of ozone,their distribution and variable concentrations are highly related to local ozone pollution control.In this study,we obtained vertical profiles of VOCs in Shanghai’s Jinshan district on 8 September and 9 September in 2016 to investigate their distribution and impact on local atmospheric oxidation in the near surface layer.Vertical samples were collected from heights between 50 m and 400 m by summa canisters using an unmanned aerial vehicle(UAV).Concentrations of VOCs(VOCs refers to the 52 species measured in this study)varied minimally below 200 m,and decreased by 21.2%from 100 m to 400 m.The concentrations of VOCs above 200 m decreased significantly in comparison to those below 200 m.The proportions of alkanes and aromatics increased from 55.2%and 30.5%to 57.3%and 33.0%,respectively.Additionally,the proportion of alkenes decreased from 13.2%to 8.4%.Toluene and m/p-xylene were the key species in the formation of SOA and ozone.Principal component analysis(PCA)revealed that the VOCs measured in this study mainly originated from industrial emissions.展开更多
Organic aerosol is formed in coal mines due to heat release and evaporation of organics from coal during the longwall operation.This frictional heating occurs when a metallic cutting bit strikes a rock.Thus formed org...Organic aerosol is formed in coal mines due to heat release and evaporation of organics from coal during the longwall operation.This frictional heating occurs when a metallic cutting bit strikes a rock.Thus formed organic aerosol can contribute significantly to the explosivity of methane/air atmosphere in coal mines.In this paper,the flammable limits for the methane-air mixtures with organic aerosol are determined.For this purpose,organic aerosol is synthesizes from the coal-tar pitch in a laboratory evaporation-nucleation flow chamber.Aerosol particles synthesized under laboratory conditions are aggregates consisting of small primary particles with the fractal-like dimension Df=2.0±0.1,which is close to Df=2.1±0.1 of coal mine aerosol.It is shown that the flammability of organic aerosol/methane mixture in air is in good agreement with the Le Chatelier additive principle.The lower ignition limit for the pure organic aerosol in air is 44 g/m^3.展开更多
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,t...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.展开更多
A modified two-dimensional Eulerian air quality model was used to simulate both the gaseous and particulate pollutant concentrations during October 21-24, 2004 in the Pearl River Delta (PRD) region, China. The most ...A modified two-dimensional Eulerian air quality model was used to simulate both the gaseous and particulate pollutant concentrations during October 21-24, 2004 in the Pearl River Delta (PRD) region, China. The most significant improvement to the model is the added capability to predict the secondary organic aerosols (SOA) concentrations because of the inclusion of the SOA formation chemistry. The meteorological input data were prepared using the CALMET meteorological model. The concentrations of aerosol-bound species such as NO3^-, NH4^+, SO4^2-, and SOA were calculated in the fine particle size range (〈2.5 μm). The results of the two-dimensional model were compared to the measurements at the ground level during the PRD Intensive Monitoring Campaign (IMC). Overall, there were good agreements between the measured and modeled concentrations of inorganic aerosol components and O3. Both the measured and the modeled results indicated that the maximum hourly O3 concentrations exceeded the China National Air Quality Standard. The predicted 24-h average SOA concentrations were in reasonable agreement with those predicted by the method of minimum OC/EC ratio.展开更多
Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were ana...Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer (FTIR). Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups (C-O), hydroxyl groups (-OH), carboxylic acid (- COOH), C-C bonding, N O bonding and C-H bonding (C H), was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer (ATOFMS). It was found that there are some differcnccs between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while kctoncs, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.展开更多
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 hum...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.展开更多
基金Project supported by the National Natural Science Foundation of China(No.20477043)the Knowledge Innovation Program of Chinese Academy of Sciences(No.KZCX2-SW-H08).*
文摘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.
基金supported by the "Strategic Priority Research Program" of the Chinese Academy of Sciences (Grant No. XDA05100100&XDB05020000)the National Natural Science Foundation of China (Grant Nos. 41230642 & 41275139)
文摘Fine particle of organic aerosol (OA), mostly arising from pollution, are abundant in Beijing. To achieve a better un- derstanding of the difference in OA in summer and autumn, a high-resolution time-of-flight aerosol mass spectrometer (HR- ToF-AMS, Aerodyne Research Inc., USA) was deployed in urban Beijing in August and October 2012. The mean OA mass concentration in autumn was 30 4-30 μg m-3, which was higher than in summer (13 4-6.9 μg m-3). The elemental anal- ysis found that OA was more aged in summer (oxygen-to-carbon (O/C) ratios were 0.41 and 0.32 for summer and autumn, respectively). Positive matrix factorization (PMF) analysis identified three and five components in summer and autumn, re- spectively. In summer, an oxygenated OA (OOA), a cooking-emission-related OA (COA), and a hydrocarbon-like OA (HOA) were indentified. Meanwhile, the OOA was separated into LV-OOA (low-volatility OOA) and SV-OOA (semi-volatile OOA); and in autumn, a nitrogen-containing OA (NOA) was also found. The SOA (secondary OA) was always the most important OA component, accounting for 55% of the OA in the two seasons. Back trajectory clustering analysis found that the origin of the air masses was more complex in summer. Southerly air masses in both seasons were associated with the highest OA loading, while northerly air masses were associated with the lowest OA loading. A preliminary study of OA components, especially the POA (primary OA), in different periods found that the HOA and COA all decreased during the National Day holiday period, and HOA decreased at weekends compared with weekdays.
基金supported by National Natural Science Foundation of China(grant No.41977332)the Natural Science Basic Research Program of Shaanxi(grant No.2021JQ-971,2022JQ-242)+1 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(grant No.XDB40000000)support of the Youth Innovation Promotion Association CAS(grant No.2020407).
文摘The concentration of PM_(2.5)has considerably reduced in recent years,but remains relatively high in China.In particular,the increasing contribution of organic compounds to PM_(2.5)generates popular pressure for further reductions,resulting in an urgent need to study organic aerosol(OA).To investigate the molecular composition and source contribution of OA in the rural area of the Guanzhong Plain,Northwest China,PM_(2.5)samples were collected during 3–23 August 2016 and 5–20 January 2017 and studied for more than 100 organic tracer compounds.The mean concentration of total measured organic compounds is 662±296 ng/m^(3)in summer and 3258±1925 ng/m^(3)in winter.Levoglucosan is the most abundant single compound found throughout the sampling period,which is a crucial tracer for biomass burning emissions,preliminary suggesting that biomass burning is an essential source of OA.In summer,organic compounds such as lipid compounds,sugar compounds,and polycyclic aromatic hydrocarbons(PAHs),more come from higher plants,wood burning,vehicle exhausts,plastic waste,and other direct emission sources.Oxygenated PAHs(OPAHs),nitrophenols,and phthalic acids more come from the atmosphere through the oxidation reaction of aromatic precursors,especially photochemical oxidation.However,in winter,most of the increases in concentrations of organic compounds are attributed to biomass burning.The analysis of a haze event(14–19 January 2017)during the winter sampling period shows that the increases in the concentration of organic compounds are unaccompanied by strong secondary formation under lower relative humidity(49.1%±13.5%).The main reason for the growth of OA in this haze event is the accumulation of primary OA(POA).The source apportionment by the positive matrix factorization(PMF)model shows that biomass burning(37.1%)is the primary source of OA in the rural regions of the Guanzhong Plain,especially in winter(40.6%).The contribution of secondary formation decreases from 26.0%in summer to 16.9%in winter,and the contribution of fossil fuel emissions is comparable across both seasons.
基金supported by the National Natural Science Foundation of China(Grant No.42177083)the Natural Science Foundation of Shandong Province(Grant No.ZR2020MD113)the Open Funds of State Key Laboratory of Loess and Quaternary Geology,Institute of Earth Environment,Chinese Academy of Sciences(Grant No.SKLLOG 2020).
文摘To better understand the seasonal characteristics of urban organic aerosol(OA)in the North China Plain(NCP),PM2.5 samples in the urban atmosphere of Liaocheng were collected and analyzed.The molecular distribution of the organic markers in the urban atmosphere of Liaocheng reveals that n-alkanes(39.3%)was the most abundant species all year round,followed by saccharides(28.2%),phthalic acids(Ph,20.8%),biogenic secondary organic aerosol(BSOA)tracers(9.4%),and polycyclic aromatic hydrocarbon(PAHs,2.3%).PM2.5,organic carbon(OC),elemental carbon(EC),and primary organic markers exhibit the highest concentrations in winter,due largely to the increased biomass burning and coal combustion for house heating in local and surrounding regions.However,the concentration and relative abundance of BSOA are significantly higher in summer than other seasons,induced by the more favorable meteoro-logical conditions that would promote the emissions of biogenic volatile organic compounds(BVOCs)and the secondary production of BSOA.The ratios of OC/EC and 3-methyl-1,2,3-butanetricarboxylic acid to cis-pinic acid plus cis-pinonic acid(MBTCA/(PA+PNA)are higher in the warm seasons than those in the cold seasons,indicating that the oxidation of OA is sensitive to air temperature.Compared to 2017,the concentration level of PAHs during wintertime decreased by 40.8%,confirming that the stringent regulation of coal burning is effective.The highest concentration of high molecular weight(HMW)n-alkanes and three anhydrosugars in winter,and the close correlation of levoglucosan with HMW n-al-kanes suggests that the impact of biomass burning was more significant in winter.The same seasonal characteristic of the ratios of high-/low-NO_(x) products with NO_(x) and the strong correlation of high-/low-NO_(x) products with levoglucosan indicate that the formation of isoprene SOA(SOA1)tracers was signif-icantly influenced by anthropogenic emissions.The molecular compositions,the distributions of fire spots,backward trajectories of air masses,and correlation analysis suggest that air pollution events in spring were primarily resulted from biomass burning and secondary oxidation,while pollution events in winter were largely driven by the increased combustion sources,and promoted aqueous secondary formation.Our results suggest that the reduction of biomass and coal combustion should be taken into account to improve the urban air quality in the NCP.
基金supported by the China National Natural Science Fund for Distinguished Young Scholars (No. 41325014)the National Key R&D Plan (Quantitative Relationship and Regulation Principle between Regional Oxidation Capacity of Atmospheric and Air Quality) (No. 2017YFC0210000)+1 种基金the program from National Nature Science Foundation of China (No. 41773117) (No. 41405122, 91543116)the West Light Foundation of Chinese Academy of Sciences
文摘Size-resolved biogenic secondary organic aerosols (BSOA) derived from isoprene and monoterpene photooxidation in Qinghai Lake, Tibetan Plateau (a continental background site) and five cities of China were measured using gas chromatography/mass spectrometry (GC/MS). Concentrations of the determined BSOA are higher in the cities than in the background and are also higher in summer than in winter. Moreover, strong positive correlations (R^2 = 0.44-0.90) between BSOA and sulfate were found at the six sites, suggesting that anthropogenic pollution (i.e., sulfate) could enhance SOA formation, because sulfate provides a surface favorable for acid-catalyzed formation of BSOA. Size distribution measurements showed that most of the determined SOA tracers are enriched in the fine mode (〈3.3 μm) except for cis-pinic and cis-pinonic acids, both presented a comparable mass in the fine and coarse (〉3.3 μm) modes, respectively. Mass ratio of oxidation products derived from isoprene to those from monoterpene in the five urban regions during summer are much less than those in Qinghai Lake region. In addition, in the five urban regions relative abundances of monoterpene oxidation products to SOA are much higher than those of isoprene. Such phenomena suggest that BSOA derived from monoterpenes are more abundant than those from isoprene in Chinese urban areas.
基金funded by the Research Council and the Faculty of Sciences of Saint Joseph University of Beirut–LebanonThe“Unitéde Chimie Environnementale et Interactions sur le Vivant”(UCEIV-UR4492)participates in the CLIMIBIO project,which is financially supported by the Hauts-de-France Region Council,the French Ministry of Higher Education and Researchthe European Regional Development Funds。
文摘Primary and secondary organic aerosols in PM_(2.5)were investigated over a one-year campaign at Zouk Mikael and Fiaa,Lebanon.The n-alkanes concentrations were quite similar at both sites(26-29 ng/m^(3))and mainly explained by anthropogenic emissions rather than natural ones.The concentrations of total Polycyclic Aromatic Hydrocarbons(PAHs)were nearly three times higher at Zouk Mikael(2.56 ng/m^(3))compared to Fiaa(0.95 ng/m^(3)),especially for indeno[1,2,3-c,d]pyrene linked to the presence of the power plant.A characteristic indeno[1,2,3-c,d]pyrene/(indeno[1,2,3-c,d]pyrene+benzo[g,h,i]perylene)ratio in the range0.8-1.0 was determined for heavy fuel oil combustion from the power plant.Fatty acids and hopanes were also investigated and were assigned to cooking activities and vehicular emissions respectively.Phthalates were identified for the first time in Lebanon with high concentrations at Zouk and Fiaa(106.88 and 97.68 ng/m^(3) respectively).Moreover,the biogenic secondary aerosols revealed higher concentrations in summer.The total terpene concentration varied between 131 ng/m^(3) at Zouk Mikael in winter to 469 ng/m3 at Fiaa in summer.Additionnally,the concentrations of the dicarboxylic acids especially for adipic and phthalic acids were more influenced by anthropogenic sources.The analysis of molecular markers and diagnostic ratios indicated that the sites were strongly affected by anthropogenic sources such as waste open burning,diesel private generators,cooking activities,road transport,power plant,and industrial emissions.Moreover,results showed different pattern during winter and summer seasons.Whereas,higher concentrations of biogenic markers were clearly encountered during the summer period.
基金National Fundamental Research Program of China (2011CB403202)National Natural Science Foundation of China (40675040)
文摘The International Centre for Theoretical Physics(ICTP,Italy) Regional Climate Model version 3.0(RegCM3) is used to simulate spatio-temporal distribution characteristics and radiative forcing(RF) of organic carbon(OC) aerosols in and around China.The preliminary simulation results show that OC aerosols are mostly concentrated in the area to the south of Yellow River and east of Tibetan Plateau.There is a decreasing trend of column burden of OC aerosols from south to north in China.The maximum value of column burden of OC aerosols is above 3 mg/m2 and located in the central and southern China,southeastern Tibet,and southwestern China's Yunnan,Guizhou,Sichuan provinces.The simulation on the seasonal variation shows that the maximum value of column burden of OC aerosols appears in winter and the secondary value is in spring and the minimum in summer.The RF of OC aerosols which varies seasonally is negative at the top of the atmosphere(TOA) and surface.The spatio-temporal characteristics of the RF of OC aerosols are basically consistent with that of IPCC,implying the high accuracy of the parameterization scheme for OC aerosols in RegCM3.
基金This work was supported by the Ministry of Science and Technology of China(Grant No.2017YFC0210004)the National Natural Science Foundation of China(Grant No.91744202)the China Postdoctoral Science Foundation and Guangdong Province Outstanding Young Talents for the International Education&Development Plan:Post-Doctoral Program.
文摘The North China Plain(NCP)is a region that experiences serious aerosol pollution.A number of studies have focused on aerosol pollution in urban areas in the NCP region;however,research on characterizing aerosols in rural NCP areas is comparatively limited.In this study,we deployed a TD-HR-AMS(thermodenuder high-resolution aerosol mass spectrometer)system at a rural site in the NCP region in summer 2013 to characterize the chemical compositions and volatility of submicron aerosols(PM_(1)).The average PM_(1)mass concentration was 51.2±48.0μg m^(−3) and organic aerosol(OA)contributed most(35.4%)to PM_(1).Positive matrix factorization(PMF)analysis of OA measurements identified four OA factors,including hydrocarbon-like OA(HOA,accounting for 18.4%),biomass burning OA(BBOA,29.4%),lessoxidized oxygenated OA(LO-OOA,30.8%)and more-oxidized oxygenated OA(MO-OOA,21.4%).The volatility sequence of the OA factors was HOA>BBOA>LO-OOA>MO-OOA,consistent with their oxygen-to-carbon(O:C)ratios.Additionally,the mean concentration of organonitrates(ON)was 1.48−3.39μg m−3,contributing 8.1%-19%of OA based on cross validation of two estimation methods with the high-resolution time-of-flight aerosol mass spectrometer(HRToF-AMS)measurement.Correlation analysis shows that ON were more correlated with BBOA and black carbon emitted from biomass burning but poorly correlated with LO-OOA.Also,volatility analysis for ON further confirmed that particulate ON formation might be closely associated with primary emissions in rural NCP areas.
基金supported by the Knowledge Innovation Foundation of Chinese Academy of Sciences (No. KJCX2-YW-N24)
文摘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.
基金This study was supported by the National Natural Science Foundation of China(No.U1706219).This is MCTL(Key Laboratory of Marine Chemistry Theory and Technology)contribution#237.
文摘Aerosols represent an important source of terrestrial organic carbon(OC)from the East Asian continent to the China marginal seas,thus their provenance and transport play important roles in the global carbon cycle.Fifty samples of total suspended particle were collected seasonally from the nearshore Huaniao Island(HNI)in East China Sea(ECS)from April 2018 to January 2019;and they were analyzed for total organic carbon(TOC)content and stable carbon isotope(δ^(13)C),as well as terrestrial bio-markers including n-alkanes(C_(20)-C_(33)),n-alkanols(C_(20)-C32)and n-fatty acids(n-FAs,C_(20)-C30),to distinguish the seasonal variabili-ties of terrestrial OC sources and reveal the influence of the long-range air mass transport on these sources.The TOC-δ^(13)C values(range from−27.3‰to−24.3‰)and molecular distributions of terrestrial biomarkers both suggested that terrestrial OC contribu-tions to aerosols had significant seasonal variations.The source indices of terrestrial biomarkers(e.g.,Fossil%=82.8%for n-alkanes)revealed that the fossil fuel OC contributions,including coal burning and vehicular emission,were higher in winter,mainly because of the long-range air mass transport from the north of the East Asian continent.The terrestrial plant OC contributions were higher in summer(e.g.,Wax%=32.4%for n-alkanes),likely due to local vegetation sources from HNI and East Asian continental air masses.Cluster analysis of air mass backward-trajectories clearly showed that transport pathway plays an important role in determining the organic constituents of aerosols in China marginal seas.A comparison of these terrestrial OC contributions from different air mass origins suggested that fossil fuel OC showed less variations among various air mass origins from northern China in winter,while terrestrial plant OC sources from northern and southern China in summer contributed more than that from the air masses transported through the ECS.These results provided a basis for future quantification of terrestrial OC from different origins in marine aerosols,by combining biomarker index and carbon isotopes.
文摘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.
基金supported by the Knowledge Innovation Foundation of Chinese Academy of Sciences (No.KJCX2-YW-N24)
文摘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.
基金This work was supported by National Natural Science Foundation of China(Grant No.91644214)Youth Innovation Program of Universities in Shandong Province(Grant No.2019KJD007)Fundamental Research Fund of Shandong University(Grant No.2020QNQT012).
文摘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.
基金the National Natural ScienceFundation of China (No. 20637001)
文摘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 ...
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.41830106,21607104)the National Key Research and Development Plan(Grant Nos.2017YFC0210004,2018YFC0213801)+1 种基金the Shanghai Science and Technology Commission of Shanghai Municipality(18QA 403600)the Shanghai Environmental Protection Bureau(2017-2).
文摘As Volatile Organic Compounds(VOCs)are one of the precursors of ozone,their distribution and variable concentrations are highly related to local ozone pollution control.In this study,we obtained vertical profiles of VOCs in Shanghai’s Jinshan district on 8 September and 9 September in 2016 to investigate their distribution and impact on local atmospheric oxidation in the near surface layer.Vertical samples were collected from heights between 50 m and 400 m by summa canisters using an unmanned aerial vehicle(UAV).Concentrations of VOCs(VOCs refers to the 52 species measured in this study)varied minimally below 200 m,and decreased by 21.2%from 100 m to 400 m.The concentrations of VOCs above 200 m decreased significantly in comparison to those below 200 m.The proportions of alkanes and aromatics increased from 55.2%and 30.5%to 57.3%and 33.0%,respectively.Additionally,the proportion of alkenes decreased from 13.2%to 8.4%.Toluene and m/p-xylene were the key species in the formation of SOA and ozone.Principal component analysis(PCA)revealed that the VOCs measured in this study mainly originated from industrial emissions.
基金RFBR and Novosibirsk region(Grant No.19-43-540009).
文摘Organic aerosol is formed in coal mines due to heat release and evaporation of organics from coal during the longwall operation.This frictional heating occurs when a metallic cutting bit strikes a rock.Thus formed organic aerosol can contribute significantly to the explosivity of methane/air atmosphere in coal mines.In this paper,the flammable limits for the methane-air mixtures with organic aerosol are determined.For this purpose,organic aerosol is synthesizes from the coal-tar pitch in a laboratory evaporation-nucleation flow chamber.Aerosol particles synthesized under laboratory conditions are aggregates consisting of small primary particles with the fractal-like dimension Df=2.0±0.1,which is close to Df=2.1±0.1 of coal mine aerosol.It is shown that the flammability of organic aerosol/methane mixture in air is in good agreement with the Le Chatelier additive principle.The lower ignition limit for the pure organic aerosol in air is 44 g/m^3.
基金National Natural Science Foundation of China (Nos.22125303,92061203,and 22288201)the National Key Research and Development Program of China (No.2021YFA1400501)+3 种基金Innovation Program for Quantum Science and Technology (No.2021ZD0303304)Dalian Institute of Chemical Physics (No.DICP DCLS201702)Chinese Academy of Sciences (No.GJJSTD20220001)K.C.Wong Education Foundation (No.GJTD-2018-06)。
文摘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.
基金Project supported by the National Natural Science Foundation of China (No. 40375038)the National Basic Research Program of China (No. 2002CB410802, 2002CB410801).
文摘A modified two-dimensional Eulerian air quality model was used to simulate both the gaseous and particulate pollutant concentrations during October 21-24, 2004 in the Pearl River Delta (PRD) region, China. The most significant improvement to the model is the added capability to predict the secondary organic aerosols (SOA) concentrations because of the inclusion of the SOA formation chemistry. The meteorological input data were prepared using the CALMET meteorological model. The concentrations of aerosol-bound species such as NO3^-, NH4^+, SO4^2-, and SOA were calculated in the fine particle size range (〈2.5 μm). The results of the two-dimensional model were compared to the measurements at the ground level during the PRD Intensive Monitoring Campaign (IMC). Overall, there were good agreements between the measured and modeled concentrations of inorganic aerosol components and O3. Both the measured and the modeled results indicated that the maximum hourly O3 concentrations exceeded the China National Air Quality Standard. The predicted 24-h average SOA concentrations were in reasonable agreement with those predicted by the method of minimum OC/EC ratio.
基金The National Natural Science Foundation of China (No. 20477043), the Knowledge Innovation Foundation of Chinese Academy ofSciences (No. KJCX2-SW-H08) and the National Synchrotron Graduation Innovation Foundation of Ministry of Education of China (Hefei)
文摘Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer (FTIR). Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups (C-O), hydroxyl groups (-OH), carboxylic acid (- COOH), C-C bonding, N O bonding and C-H bonding (C H), was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer (ATOFMS). It was found that there are some differcnccs between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while kctoncs, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.
基金supported by the Central Level,Scientific Research Institutes for Basic R&D Special Fund Business,China(No.2021-JY-16)the National Natural Science Foundation of China(Nos.42075182 and 2130721)+1 种基金the National Research Program for Key Issue in Air Pollution Control(No.DQGG2021101)the National Key Research and Development Program of China(No.2019YFC0214800)。
文摘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.