Quantifying differences in secondary organic aerosols(SOAs)between the preindustrial period and the present day is crucial to assess climate forcing and environmental effects resulting from anthropogenic activities.Th...Quantifying differences in secondary organic aerosols(SOAs)between the preindustrial period and the present day is crucial to assess climate forcing and environmental effects resulting from anthropogenic activities.The lack of vegetation information for the preindustrial period and the uncertainties in describing SOA formation are two leading factors preventing simulation of SOA.This study calculated the online emissions of biogenic volatile organic compounds(VOCs)in the Aerosol and Atmospheric Chemistry Model of the Institute of Atmospheric Physics(IAP-AACM)by coupling the Model of Emissions of Gases and Aerosols from Nature(MEGAN),where the input vegetation parameters were simulated by the IAP Dynamic Global Vegetation Model(IAP-DGVM).The volatility basis set(VBS)approach was adopted to simulate SOA formation from the nontraditional pathways,i.e.,the oxidation of intermediate VOCs and aging of primary organic aerosol.Although biogenic SOAs(BSOAs)were dominant in SOAs globally in the preindustrial period,the contribution of nontraditional anthropogenic SOAs(ASOAs)to the total SOAs was up to 35.7%.In the present day,the contribution of ASOAs was 2.8 times larger than that in the preindustrial period.The contribution of nontraditional sources of SOAs to SOA was as high as 53.1%.The influence of increased anthropogenic emissions in the present day on BSOA concentrations was greater than that of increased biogenic emission changes.The response of BSOA concentrations to anthropogenic emission changes in the present day was more sensitive than that in the preindustrial period.The nontraditional sources and the atmospheric oxidation capability greatly affect the global SOA change.展开更多
In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists ...In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists of the collapsible ~830 L FEP Teflon film main reactor, in which the atmospheric chemical reactions take place and the formation of SOA occurs under the simulated atmospheric conditions, and the diverse on-line gas- and particle-phase instrumentation, such as the proton transfer reaction mass spectrometer, the synchrotron radiation photoionization mass spectrometer, the aerosol laser time-of-flight mass spectrometer, and other traditional commercial instruments. The initial characterization experiments are described, concerning the temperature and ultraviolet light intensity, the reactivity of the pure air, the wall loss rates of gaseous compounds and particulate matter. And the initial evaluation experiments for SOA yields from the ozonolysis of α-pinene and for mass spectra of the products resulting from the photooxidation of OH initiated isoprene are also presented, which indicate the applicability of this facility on the studies of gas-phase chemical mechanisms as well as the formation of SOA expected in the atmosphere.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
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
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
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
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
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
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
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
The regional air quality modeling system RAMS-CMAQ was updated to incorporate secondary organic aerosol (SOA) production from isoprene and sesquiterpene and to account for the SOA production rate dependence on NOx a...The regional air quality modeling system RAMS-CMAQ was updated to incorporate secondary organic aerosol (SOA) production from isoprene and sesquiterpene and to account for the SOA production rate dependence on NOx and SOA aging. The system was then used to simulate spatiotemporal distributions of SOA concentration and its major constituents over China in winter. Modeled monthly mean SOA concentrations were high in central and eastern China and low in western regions. The highest SOA appeared in regions from Beijing-Tianjin-Hebei (BTH) to the middle reaches of the Yangtze River and areas from Sichuan Basin to the southwest border of China, where SOA contributions were less than 10% of the organic aerosol (OA). The lowest concentration was in the Qinghai-Tibet Plateau, accounting for 20%-30% of OA. It is notable that contributions from anthropogenic precursors to SOA were significant in winter, especially the wide areas of central and eastern China with contributions generally varying from 50% to 80% of the total SOA. Beijing was used as an example location representative of the heavily polluted BTH area for analysis of major components of SOA. Though the modeled concentration of SOA was still underestimated compared to the observations, it still showed that xylene and toluene were the two greatest contributors to anthropogenic SOA, which was in agreement with the observations. SOA produced from monoterpene was the greatest contributor to biogenic SOA due to the high mass yield of monoterpene, followed by isoprene. More than 57% of SOAs were aged, which may increase the extinction effect of SOA.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
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
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
Unsaturated ketones are typical oxygenated volatile organic compounds(OVOCs)with high reactivity,and are important precursors in air pollution.The sources of OVOCs are complex and include direct emissions and secondar...Unsaturated ketones are typical oxygenated volatile organic compounds(OVOCs)with high reactivity,and are important precursors in air pollution.The sources of OVOCs are complex and include direct emissions and secondary oxidation formation of VOCs in the atmosphere.2-Cyclohexen-1-one is a widespread substance,and is derived from the industrial catalytic oxidation of cyclohexene.In this paper,we investigated the rate constants of the chemical reactions of 2-cyclohexen-1-one with NO_(3) radicals,which is(7.25±0.29)×10^(-15) cm^(3)·molecule^(-1)·s^(-1) at 298 K and under 1 atm(1 atm=101325Pa).It supplemented the kinetics of NO_(3) radicals database,and revealed its effects in the nighttime atmosphere.In addition,the reaction products of 2-cyclohexen-1-one with NO_(3) radicals were detected by Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS),which revealed a series of nitrate esters in the composition of the secondary organic aerosol(SOA),which may reduce atmospheric visibility.Finally,the possible pathways for the generation of the products were developed.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
Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants whi...Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants which further affects secondary OA formation.Here we provide an observational analysis of secondary OA(SOA)variation properties in Yangtze River Delta(YRD)of eastern China in response to large scale of emission reduction during Chinese New Year(CNY)holidays from 2015 to 2020,and the COVID-19 pandemic period from January to March,2020.We found a 17%increase of SOA proportion during the COVID lockdown.The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions.Two types of oxygenated OA(OOA)influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region.Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures.展开更多
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 reaction...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.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
PM_(1)0 samples were collected from an urban/industrial site nearby Athens,where uncontrolled burning activities occur.PAHs,monocarboxylic,dicarboxylic,hydroxycarboxylic and aromatic acids,tracers from BVOC oxidation,...PM_(1)0 samples were collected from an urban/industrial site nearby Athens,where uncontrolled burning activities occur.PAHs,monocarboxylic,dicarboxylic,hydroxycarboxylic and aromatic acids,tracers from BVOC oxidation,biomass burning tracers and bisphenol A were determined.PAH,monocarboxylic acids,biomass burning tracers and bisphenol A were increased during autumn/winter,while BSOA tracers,dicarboxylic-and hydroxycarboxylic acids during summer.Regarding aromatic acids,different sources and formation mechanisms were indicated as benzoic,phthalic and trimellitic acids were peaked during summer whereas p-toluic,isophthalic and terephthalic were more abundant during autumn/winter.The Benzo[a]pyrene-equivalent carcinogenic power,carcinogenic and mutagenic activities were calculated showing significant(p<0.05)increases during the colder months.Palmitic,succinic and malic acids were the most abundant monocarboxylic,dicarboxylic and hydrocarboxylic acids during the entire sampling period.Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA(13.4±12.3 and 6.1±2.9 ng/m^3,respectively).Ozone has significant impact on the formation of many studied compounds showing significant correlations with:isoprene-SOA(r=0.77),hydrocarboxylic acids(r=0.69),pinene-SOA(r=0.63),dicarboxylic acids(r=0.58),and the sum of phthalic,benzoic and trimellitic acids(r=0.44).PCA demonstrated five factors that could explain sources including plastic enriched waste burning(30.8%),oxidation of unsaturated fatty acids(23.0%),vehicle missions and cooking(9.2%),biomass burning(7.7%)and oxidation of VOCs(5.8%).The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.展开更多
基金supported by the National Key R&D Program of China(Grant No.2020YFA0607801)the National Natural Science Foundation of China(Grant Nos.42007199 and 42377105)the National Key Scientific and Technological Infrastructure project“Earth System Science Numerical Simulator Facility”.
文摘Quantifying differences in secondary organic aerosols(SOAs)between the preindustrial period and the present day is crucial to assess climate forcing and environmental effects resulting from anthropogenic activities.The lack of vegetation information for the preindustrial period and the uncertainties in describing SOA formation are two leading factors preventing simulation of SOA.This study calculated the online emissions of biogenic volatile organic compounds(VOCs)in the Aerosol and Atmospheric Chemistry Model of the Institute of Atmospheric Physics(IAP-AACM)by coupling the Model of Emissions of Gases and Aerosols from Nature(MEGAN),where the input vegetation parameters were simulated by the IAP Dynamic Global Vegetation Model(IAP-DGVM).The volatility basis set(VBS)approach was adopted to simulate SOA formation from the nontraditional pathways,i.e.,the oxidation of intermediate VOCs and aging of primary organic aerosol.Although biogenic SOAs(BSOAs)were dominant in SOAs globally in the preindustrial period,the contribution of nontraditional anthropogenic SOAs(ASOAs)to the total SOAs was up to 35.7%.In the present day,the contribution of ASOAs was 2.8 times larger than that in the preindustrial period.The contribution of nontraditional sources of SOAs to SOA was as high as 53.1%.The influence of increased anthropogenic emissions in the present day on BSOA concentrations was greater than that of increased biogenic emission changes.The response of BSOA concentrations to anthropogenic emission changes in the present day was more sensitive than that in the preindustrial period.The nontraditional sources and the atmospheric oxidation capability greatly affect the global SOA change.
基金This work was supported by the Natural Science Foundation of Anhui Province, China (No.1208085MD59), the National Natural Science Foundation of China (No.U1232209, No.41175121, and No.21307137), the Presidential Foundation of Hefei Institutes of Physical Science, Chinese Academy of Sciences, China (No.YZJJ201302), and the Knowledge Innovation Foundation of the Chinese Academy of Sciences (No.KJCX2-YW-N24).
文摘In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists of the collapsible ~830 L FEP Teflon film main reactor, in which the atmospheric chemical reactions take place and the formation of SOA occurs under the simulated atmospheric conditions, and the diverse on-line gas- and particle-phase instrumentation, such as the proton transfer reaction mass spectrometer, the synchrotron radiation photoionization mass spectrometer, the aerosol laser time-of-flight mass spectrometer, and other traditional commercial instruments. The initial characterization experiments are described, concerning the temperature and ultraviolet light intensity, the reactivity of the pure air, the wall loss rates of gaseous compounds and particulate matter. And the initial evaluation experiments for SOA yields from the ozonolysis of α-pinene and for mass spectra of the products resulting from the photooxidation of OH initiated isoprene are also presented, which indicate the applicability of this facility on the studies of gas-phase chemical mechanisms as well as the formation of SOA expected in the atmosphere.
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 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 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supported by the‘Strategic Priority Research Program(B)’of the Chinese Academy of Sciences[XDB05030105],[XDB05030102],[XDB05030103]the National Basic Research Program of China[2014CB953802]
文摘The regional air quality modeling system RAMS-CMAQ was updated to incorporate secondary organic aerosol (SOA) production from isoprene and sesquiterpene and to account for the SOA production rate dependence on NOx and SOA aging. The system was then used to simulate spatiotemporal distributions of SOA concentration and its major constituents over China in winter. Modeled monthly mean SOA concentrations were high in central and eastern China and low in western regions. The highest SOA appeared in regions from Beijing-Tianjin-Hebei (BTH) to the middle reaches of the Yangtze River and areas from Sichuan Basin to the southwest border of China, where SOA contributions were less than 10% of the organic aerosol (OA). The lowest concentration was in the Qinghai-Tibet Plateau, accounting for 20%-30% of OA. It is notable that contributions from anthropogenic precursors to SOA were significant in winter, especially the wide areas of central and eastern China with contributions generally varying from 50% to 80% of the total SOA. Beijing was used as an example location representative of the heavily polluted BTH area for analysis of major components of SOA. Though the modeled concentration of SOA was still underestimated compared to the observations, it still showed that xylene and toluene were the two greatest contributors to anthropogenic SOA, which was in agreement with the observations. SOA produced from monoterpene was the greatest contributor to biogenic SOA due to the high mass yield of monoterpene, followed by isoprene. More than 57% of SOAs were aged, which may increase the extinction effect of SOA.
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(Nos.42130606,42022039)the Fund of the Beijing National Laboratory for Molecular Sciences China(No.BNLMS-CXXM-202011)the Project of the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.Y2021013).
文摘Unsaturated ketones are typical oxygenated volatile organic compounds(OVOCs)with high reactivity,and are important precursors in air pollution.The sources of OVOCs are complex and include direct emissions and secondary oxidation formation of VOCs in the atmosphere.2-Cyclohexen-1-one is a widespread substance,and is derived from the industrial catalytic oxidation of cyclohexene.In this paper,we investigated the rate constants of the chemical reactions of 2-cyclohexen-1-one with NO_(3) radicals,which is(7.25±0.29)×10^(-15) cm^(3)·molecule^(-1)·s^(-1) at 298 K and under 1 atm(1 atm=101325Pa).It supplemented the kinetics of NO_(3) radicals database,and revealed its effects in the nighttime atmosphere.In addition,the reaction products of 2-cyclohexen-1-one with NO_(3) radicals were detected by Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS),which revealed a series of nitrate esters in the composition of the secondary organic aerosol(SOA),which may reduce atmospheric visibility.Finally,the possible pathways for the generation of the products were developed.
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.
基金supported by National Natural Science Foundation of China(No.42005082).
文摘Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants which further affects secondary OA formation.Here we provide an observational analysis of secondary OA(SOA)variation properties in Yangtze River Delta(YRD)of eastern China in response to large scale of emission reduction during Chinese New Year(CNY)holidays from 2015 to 2020,and the COVID-19 pandemic period from January to March,2020.We found a 17%increase of SOA proportion during the COVID lockdown.The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions.Two types of oxygenated OA(OOA)influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region.Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures.
基金financially supported by the Natural Science Foundation of Guangdong Province,China (No.2019B151502064)the National Natural Science Foundation of China (Nos.42077189 and 4201001008)+2 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No.2017BT01Z032)the Innovation Team Project of Guangdong Provincial Department of Education(No.2017KCXTD012)the Science and Technology Key Project of Guangdong Province,China (No.2019B110206002)。
文摘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.
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.
文摘PM_(1)0 samples were collected from an urban/industrial site nearby Athens,where uncontrolled burning activities occur.PAHs,monocarboxylic,dicarboxylic,hydroxycarboxylic and aromatic acids,tracers from BVOC oxidation,biomass burning tracers and bisphenol A were determined.PAH,monocarboxylic acids,biomass burning tracers and bisphenol A were increased during autumn/winter,while BSOA tracers,dicarboxylic-and hydroxycarboxylic acids during summer.Regarding aromatic acids,different sources and formation mechanisms were indicated as benzoic,phthalic and trimellitic acids were peaked during summer whereas p-toluic,isophthalic and terephthalic were more abundant during autumn/winter.The Benzo[a]pyrene-equivalent carcinogenic power,carcinogenic and mutagenic activities were calculated showing significant(p<0.05)increases during the colder months.Palmitic,succinic and malic acids were the most abundant monocarboxylic,dicarboxylic and hydrocarboxylic acids during the entire sampling period.Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA(13.4±12.3 and 6.1±2.9 ng/m^3,respectively).Ozone has significant impact on the formation of many studied compounds showing significant correlations with:isoprene-SOA(r=0.77),hydrocarboxylic acids(r=0.69),pinene-SOA(r=0.63),dicarboxylic acids(r=0.58),and the sum of phthalic,benzoic and trimellitic acids(r=0.44).PCA demonstrated five factors that could explain sources including plastic enriched waste burning(30.8%),oxidation of unsaturated fatty acids(23.0%),vehicle missions and cooking(9.2%),biomass burning(7.7%)and oxidation of VOCs(5.8%).The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.