Contrast in Secondary Organic Aerosols between the Present Day and the Preindustrial Period:The Importance of Nontraditional Sources and the Changed Atmospheric Oxidation Capability

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.

A Smog Chamber Facility for Qualitative and Quantitative Study on Atmospheric Chemistry and Secondary Organic Aerosol

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.

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

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

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

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

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

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

Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation

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

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

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

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

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

Reaction Kinetics and Secondary Organic Aerosol Composition Analysis of 2-Cyclohexen-1-one with NO_(3) Radicals

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.

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

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

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

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

Source apportionment and secondary organic aerosol estimation of PM_(2.5) in an urban atmosphere in China

PM2.5 is the key pollutant in atmospheric pollution in China.With new national air quality standards taking effect,PM2.5 has become a major issue for future pollution control.To effectively prevent and control PM2.5,its emission sources must be precisely and thoroughly understood.However,there are few publications reporting comprehensive and systematic results of PM2.5 source apportionment in the country.Based on PM2.5 sampling during 2009 in Shenzhen and follow-up investigation,positive matrix factorization(PMF)analysis has been carried out to understand the major sources and their temporal and spatial variations.The results show that in urban Shenzhen(University Town site),annual mean PM2.5 concentration was 42.2μg m?3,with secondary sulfate,vehicular emission,biomass burning and secondary nitrate as major sources;these contributed30.0%,26.9%,9.8%and 9.3%to total PM2.5,respectively.Other sources included high chloride,heavy oil combustion,sea salt,dust and the metallurgical industry,with contributions between 2%–4%.Spatiotemporal variations of various sources show that vehicular emission was mainly a local source,whereas secondary sulfate and biomass burning were mostly regional.Secondary nitrate had both local and regional sources.Identification of secondary organic aerosol(SOA)has always been difficult in aerosol source apportionment.In this study,the PMF model and organic carbon/elemental carbon(OC/EC)ratio method were combined to estimate SOA in PM2.5.The results show that in urban Shenzhen,annual SOA mass concentration was 7.5μg m?3,accounting for 57%of total organic matter,with precursors emitted from vehicles as the major source.This work can serve as a case study for further in-depth research on PM2.5 pollution and source apportionment in China.

Comparative investigation of coal-and oil-fired boilers based on emission factors,ozone and secondary organic aerosol formation potentials of VOCs

Volatile organic compounds(VOCs)are the important precursors of the tropospheric ozone(O3)and secondary organic aerosols(SOA),both of which are known to harm human health and disrupt the earth’s climate system.In this study,VOC emission factors,O3 and SOA formation potentials were estimated for two types of industrial boilers:coal-fired boilers(n=3)and oil-fired boilers(n=3).Results showed that EVOCs concentrations were more than nine times higher for oil-fire d boilers compared to those for coal-fired boilers.Emission factors ofΣVOCs were found to be higher for oil-fired boilers(9.26-32.83 mg-VOC/kg)than for coal-fired boilers(1.57-4.13 mg-VOC/kg).Alkanes and aromatics were obtained as the most abundant groups in coal-fired boilers,while oxygenated organics and aromatics were the most contributing groups in oil-fired boilers.Benzene,n-hexane and o-ethyl toluene were the abundant VOC species in coal-fired boiler emissions,whereas toluene was the most abundant VOC species emitted from oil-fired boilers.O3 and SOA formation potentials were found 12 and 18 times,respectively,higher for oil-fired than for coal-fired boilers.Total OFP ranged from 3.99 to 11.39 mg-O3/kg for coal-fired boilers.For oil-fired boilers,total OFP ranged from 36.16 to 131.93 mg-O3/kg.Moreover,total secondary organic aerosol potential(SOAP)ranged from 65.4 to 122.5 mg-SOA/kg and 779.9 to 2252.5 mg-SOA/kg for the coal-fired and oil-fired boilers,respectively.

Seasonal variation and size distribution of biogenic secondary organic aerosols at urban and continental background sites of China

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.

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning

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.

Real-time detection of individual secondary organic aerosol particle from photooxidation of toluene using aerosol time of flight mass spectrometer

Photooxidation of the aromatic hydrocarbon toluene and its subsequent reactions were carried out using UV-irradiation of toluene/CH_(3)ONO/NO/air mixtures in a home-made smog chamber.The secondary organic aerosols could be formed after those oxidation products of semi-volatile or-ganic compounds were partitioned between gas phase and particle phase.The aerosol time of flight mass spectrometer(ATOFMS)was used to measure size and molecular composition of individual secondary organic aerosol particle.Size distribution and chemical composition of secondary organic aerosol were got in real time.

WRF/CHEM modeling of impacts of weather conditions modified by urban expansion on secondary organic aerosol formation over Pearl River Delta

In this paper, the online Weather Research and Forecasting and Chemistry （WRF/CHEM） model, coupled with urban canopy （UCM） and biogenic-emission models, is used to explore impacts of urban expansion on secondary organic aerosols （SOA） formation. Two scenarios of urban maps are used in WRF/CHEM to represent early 1990s （pre-urbanization） and current urban distribution in the Pearl River Delta （PRD）. Month-long simulation results using the above land-use scenarios for March 2001 show： （1） urbanization can increase monthly averaged temperatures by about 0.63 ℃, decrease monthly averaged 10-m wind speeds by 38%, increase monthly averaged boundary-layer depths by 80 m, and decrease monthly aver- aged water mixing ratio by 0.2g/kg. （2） Changes in meteorological conditions can result in detectable concentration changes of NOx, VOC, O3 and NO3 radicals. Urbanization decreases surface NOx and VOC concentrations by a maximum of 4 ppbv and 1.5 ppbv, respectively. Surface O3 and NO3 radical concentrations over major cities increase by about 2-4 ppbv and 4-12 pptv, respectively; areas with increasing O3 and NO3 radical concentrations generally coincide with the areas of temperature increase and wind speed reduction where NOx and VOC decrease. （3） Urbanization can induce 9% increase of SOA in Foshan, Zhongshan and west Guangzhou and 3% decrease in Shenzhen and Dongguan. Over PRD major cities, SOA from Aitken mode reduces by 30% but with more than 70% SOA from accumulate mode. Urbanization has stronger influence on SOA formation from Aitken mode. （4） Over the PRD, 55-65% SOA comes from aromatics precursors. Urbanization has strongest influence on aromatics precursors to produce SOA （14% increase）, while there is less influence on alkane precursors. Alkene precursors have negative contribution to SOA formation under urbanization situation.

Roles of semivolatile and intermediate-volatility organic compounds in secondary organic aerosol formation and its implication:A review

Secondary organic aerosol(SOA)is a very important component of fine particulate matter(PM)in the atmosphere.However,the simulations of SOA,which could help to elucidate the detailed mechanism of SOA formation and quantify the roles of various precursors,remains unsatisfactory,as SOA levels are frequently underestimated.It has been found that the performance of SOA formation models can be significantly improved by incorporating the emission and evolution of semivolatile and intermediate-volatility organic compounds(S/IVOCs).In order to explore the roles of S/IVOCs in SOA formation,this study reviews some simulation models which could consider S/IVOCs for SOA formation as well as the development of emission inventories of S/IVOCs and S/IVOC modules for SOA formation.In addition,the future research directions for simulations of the effect of S/IVOCs on SOA formation are suggested.

Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

Secondary organic aerosol （SOA） formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber. The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer （ALTOFMS）, respectively. According to a large number of single aerosol diameter and mass spectra, the size distribution and chemical composition of SOA were obtained statistically. Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles, which have diameters less than 2.5 μm （i.e., PM2.5）, and glyoxal, benzaldehyde, benzyl alcohol, benzoquinone, benzoic acid, benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA. The possible reaction mechanisms leading to these products are also proposed.

Characterization of particulate products for aging of ethylbenzene secondary organic aerosol in the presence of ammonium sulfate seed aerosol

Aging of secondary organic aerosol（SOA） particles formed from OH– initiated oxidation of ethylbenzene in the presence of high mass（100–300 μg/m^3） concentrations of（NH_4）_2SO_4seed aerosol was investigated in a home-made smog chamber in this study.The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer（ALTOFMS） coupled with a Fuzzy C-Means（FCM） clustering algorithm.Experimental results showed that nitrophenol,ethyl-nitrophenol,2,4-dinitrophenol,methyl glyoxylic acid,5-ethyl-6-oxo-2,4-hexadienoic acid,2-ethyl-2,4-hexadiendioic acid,2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid,1H-imidazole,hydrated N-glyoxal substituted1H-imidazole,hydrated glyoxal dimer substituted imidazole,1H-imidazole-2-carbaldehyde,N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight（HMW） components were the predominant products in the aged particles.Compared to the previous aromatic SOA aging studies,imidazole compounds,which can absorb solar radiation effectively,were newly detected in aged ethylbenzene SOA in the presence of high concentrations of（NH_4）_2SO_4seed aerosol.These findings provide new information for discussing aromatic SOA aging mechanisms.