大气有机气溶胶（OA）老化过程的在线观测是气溶胶化学研究领域的难点之一.本研究应用颗粒物化学组分监测仪（ACSM）对南京夏季城区大气非难熔性亚微米细颗粒物（NR-PM1）组分进行在线连续观测,并利用ACSM观测出的特征碎片离子,即f44（m...大气有机气溶胶（OA）老化过程的在线观测是气溶胶化学研究领域的难点之一.本研究应用颗粒物化学组分监测仪（ACSM）对南京夏季城区大气非难熔性亚微米细颗粒物（NR-PM1）组分进行在线连续观测,并利用ACSM观测出的特征碎片离子,即f44（m/z 44与总OA的质谱信号之比）与f57（m/z 57与总OA的质谱信号之比）间的函数关系（f44 vs f57）及变化规律来动态估计大气中烃类有机气溶胶（HOA）的老化过程.结果表明：观测期间NR-PM1平均质量浓度为19.87±8.46μg m-3,其中OA占比最大（51.8%）,且OA中氧化态有机气溶胶（OOA）的贡献较大（72%±0.14%）.OOA,Ox（Ox=O3＋NO2）的质量浓度与OOA/ΔCO（ΔCO是去除CO背景值后的质量浓度）呈相似的日变化规律,表明OOA的生成过程主要受大气光化学活性的影响.在f44 vs f57中,OOA/ΔCO和Ox质量浓度随f44的增大而逐渐增大,而HOA/ΔCO和HOA/OA的大小随f44的增大逐渐减小.这些特征反映出HOA通过光化学反应作用逐渐向OOA转化的过程.此外,利用f57的变化规律估算大气中HOA所需的老化时间约为5～10 h.本文为外场观测中动态长期地研究大气气溶胶的老化进程及其寿命提供一种新思路和方法.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
The surface tension of troposphere aerosols can significantly influence their atmospheric processes and key properties, particularly on the morphology, the phase transition, the activation as cloud condensation nuclei...The surface tension of troposphere aerosols can significantly influence their atmospheric processes and key properties, particularly on the morphology, the phase transition, the activation as cloud condensation nuclei, and the gas-particle partitioning. However, directly measuring the surface tension of single ambient aerosol is quite challenging, due to the limitations of their picolitre volumes and thermal motion. Here, we developed a dual laser tweezers Raman spectroscopy(DLT-RS) system to directly sense the surface tension of single airborne microdroplets(PM10particles). A pair of aerosol droplets were trapped and driven to coalesce by the laser tweezers. Meanwhile, the backscattering light intensity and brightfield images during the coalescence process were recorded to characterize the aerosol surface tension. A remarkable advantage of directly sensing aerosol surface tension is that the solutes in aerosols are often supersaturated, which is common in atmospheric aerosols but almost unavailable in bulk solutions.We experimentally measured the surface tension of aerosols composed of nitrates or oxalic acid/nitrate mixture. Besides, the variation of surface tension during aerosol aging process was also explored, which brings possible implications on the surface evolution of actual ambient aerosol during their atmospheric lifetime.展开更多
As a main form of biomass burning in agricultural countries, crop residue burning is a significant source of atmospheric fine particles. In this study, the aging of particles emitted from the burning of four major cro...As a main form of biomass burning in agricultural countries, crop residue burning is a significant source of atmospheric fine particles. In this study, the aging of particles emitted from the burning of four major crop residues in China was investigated in a smog chamber.The particle size distribution, chemical composition and cloud condensation nuclei(CCN)activity were simultaneously measured. The properties of crop residue burning particles varied substantially among different fuel types. During aging, the particle size and mass concentration increased substantially, suggesting condensational growth by formation of secondary aerosols. The particle composition was dominated by organics. Aging resulted in considerable enhancement of organics and inorganics, with enhancement ratios of 1.24–1.44 and 1.33–1.76 respectively, as well as a continuous increase in the oxidation level of organics. Elevated CCN activity was observed during aging, with the hygroscopicity parameter κ varying from 0.16 to 0.34 for fresh particles and 0.19 to 0.40 for aged particles.Based on the volume mixing rule, the hygroscopicity parameter of organic components(κorg) was derived. κorgexhibited an increasing tendency with aging, which was generally consistent with the tendency of the O:C ratio, indicating that the oxidation level was related to the hygroscopicity and CCN activity of organic aerosols from crop residue burning. Our results indicated that photochemical aging could significantly impact the CCN activation of crop burning aerosols, not only by the production of secondary aerosols, but also by enhancing the hygroscopicity of organic components, thereby contributing to the aerosol indirect climate forcing.展开更多
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...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.展开更多
Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of par...Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer （TDMA） in terms of hygroscopic growth factor （Gf）, with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols （SOA） formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor （ACSM） and matrix factorization （PMF） method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.展开更多
In order to evaluate the secondary aerosol formation potential at a suburban site of Beijing,in situ perturbation experiments in a potential aerosol mass（PAM） reactor were carried out in the winter of 2014.The varia...In order to evaluate the secondary aerosol formation potential at a suburban site of Beijing,in situ perturbation experiments in a potential aerosol mass（PAM） reactor were carried out in the winter of 2014.The variations of secondary aerosol formation as a function of time,OH exposure,and the concentrations of gas phase pollutants and particles were reported in this study.Two periods with distinct secondary aerosol formation potentials,marked as Period Ⅰ and Period Ⅱ,were identified during the observation.In Period Ⅰ,the secondary aerosol formation potential was high,and correlated well to the air pollutants,i.e.,SO2,NO2,and CO.The maximal secondary aerosol formation was observed with an aging time equivalent to about 3 days of atmospheric oxidation.In period Ⅱ,the secondary aerosol formation potential was low,with no obvious correlation with the air pollutants.Meanwhile,the aerosol mass decreased,instead of showing a peak,with increasing aging time.Backward trajectory analysis during the two periods confirmed that the air mass in Period Ⅰwas mainly from local sources,while it was attributed mostly to long distance transport in Period Ⅱ.The air lost its reactivity during the long transport and the particles became highly aged,resulting in a low secondary aerosol formation potential.Our experimental results indicated that the in situ measurement of the secondary aerosol formation potential could provide important information for evaluating the contributions of local emission and long distance transport to the aerosol pollution.展开更多
文摘大气有机气溶胶（OA）老化过程的在线观测是气溶胶化学研究领域的难点之一.本研究应用颗粒物化学组分监测仪（ACSM）对南京夏季城区大气非难熔性亚微米细颗粒物（NR-PM1）组分进行在线连续观测,并利用ACSM观测出的特征碎片离子,即f44（m/z 44与总OA的质谱信号之比）与f57（m/z 57与总OA的质谱信号之比）间的函数关系（f44 vs f57）及变化规律来动态估计大气中烃类有机气溶胶（HOA）的老化过程.结果表明：观测期间NR-PM1平均质量浓度为19.87±8.46μg m-3,其中OA占比最大（51.8%）,且OA中氧化态有机气溶胶（OOA）的贡献较大（72%±0.14%）.OOA,Ox（Ox=O3＋NO2）的质量浓度与OOA/ΔCO（ΔCO是去除CO背景值后的质量浓度）呈相似的日变化规律,表明OOA的生成过程主要受大气光化学活性的影响.在f44 vs f57中,OOA/ΔCO和Ox质量浓度随f44的增大而逐渐增大,而HOA/ΔCO和HOA/OA的大小随f44的增大逐渐减小.这些特征反映出HOA通过光化学反应作用逐渐向OOA转化的过程.此外,利用f57的变化规律估算大气中HOA所需的老化时间约为5～10 h.本文为外场观测中动态长期地研究大气气溶胶的老化进程及其寿命提供一种新思路和方法.
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 the National Natural Science Foundation of China (Nos.U19A2007, 32150026 and 92043302)。
文摘The surface tension of troposphere aerosols can significantly influence their atmospheric processes and key properties, particularly on the morphology, the phase transition, the activation as cloud condensation nuclei, and the gas-particle partitioning. However, directly measuring the surface tension of single ambient aerosol is quite challenging, due to the limitations of their picolitre volumes and thermal motion. Here, we developed a dual laser tweezers Raman spectroscopy(DLT-RS) system to directly sense the surface tension of single airborne microdroplets(PM10particles). A pair of aerosol droplets were trapped and driven to coalesce by the laser tweezers. Meanwhile, the backscattering light intensity and brightfield images during the coalescence process were recorded to characterize the aerosol surface tension. A remarkable advantage of directly sensing aerosol surface tension is that the solutes in aerosols are often supersaturated, which is common in atmospheric aerosols but almost unavailable in bulk solutions.We experimentally measured the surface tension of aerosols composed of nitrates or oxalic acid/nitrate mixture. Besides, the variation of surface tension during aerosol aging process was also explored, which brings possible implications on the surface evolution of actual ambient aerosol during their atmospheric lifetime.
基金四川三联新材料有限公司、四川省新型烟草制品工程技术研究中心及卷烟减害降焦四川省重点实验室科研项目“加热不燃烧气溶胶特性及检测方法研究”(JL/SCSL G J001-03)四川省科技厅重点项目“低温产香材料的研究与应用”(2018GZ0546)国家烟草专卖局重大专项项目“基于多级相变的加热卷烟烟支降温材料研究及应用”(110202101021)。
基金supported by the National Key Research and Development Project(No.2016YFC0202402)the National Natural Science Foundation of China(Nos.41575122 and 41675126)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘As a main form of biomass burning in agricultural countries, crop residue burning is a significant source of atmospheric fine particles. In this study, the aging of particles emitted from the burning of four major crop residues in China was investigated in a smog chamber.The particle size distribution, chemical composition and cloud condensation nuclei(CCN)activity were simultaneously measured. The properties of crop residue burning particles varied substantially among different fuel types. During aging, the particle size and mass concentration increased substantially, suggesting condensational growth by formation of secondary aerosols. The particle composition was dominated by organics. Aging resulted in considerable enhancement of organics and inorganics, with enhancement ratios of 1.24–1.44 and 1.33–1.76 respectively, as well as a continuous increase in the oxidation level of organics. Elevated CCN activity was observed during aging, with the hygroscopicity parameter κ varying from 0.16 to 0.34 for fresh particles and 0.19 to 0.40 for aged particles.Based on the volume mixing rule, the hygroscopicity parameter of organic components(κorg) was derived. κorgexhibited an increasing tendency with aging, which was generally consistent with the tendency of the O:C ratio, indicating that the oxidation level was related to the hygroscopicity and CCN activity of organic aerosols from crop residue burning. Our results indicated that photochemical aging could significantly impact the CCN activation of crop burning aerosols, not only by the production of secondary aerosols, but also by enhancing the hygroscopicity of organic components, thereby contributing to the aerosol indirect climate forcing.
基金supported by the National Natural Science Foundation of China (Nos.41575118,41305109,21502086,41575126)the Outstanding Youth Science Foundation of Fujian Province of China (No.2015J06009)the Natural Science Foundation of Fujian Province of China (No.2015J05028)
文摘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.
基金supported by the National Natural Science Foundation of China(No.20937004,21107060,21190054)the"Strategic Priority Research Program"of the Chinese Academy of Sciences(No.XDB05010102)supported by Toyota Motor Corporation and Toyota Central Research and Development Laboratories Inc
文摘Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer （TDMA） in terms of hygroscopic growth factor （Gf）, with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols （SOA） formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor （ACSM） and matrix factorization （PMF） method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.
基金supported by the Key Research Program of Chinese Academy of Sciences (No. KJZD-EW-TZ-G06-01-15)the National Natural Science Foundation of China (No. 21407158)the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (No. XDB05010300)
文摘In order to evaluate the secondary aerosol formation potential at a suburban site of Beijing,in situ perturbation experiments in a potential aerosol mass（PAM） reactor were carried out in the winter of 2014.The variations of secondary aerosol formation as a function of time,OH exposure,and the concentrations of gas phase pollutants and particles were reported in this study.Two periods with distinct secondary aerosol formation potentials,marked as Period Ⅰ and Period Ⅱ,were identified during the observation.In Period Ⅰ,the secondary aerosol formation potential was high,and correlated well to the air pollutants,i.e.,SO2,NO2,and CO.The maximal secondary aerosol formation was observed with an aging time equivalent to about 3 days of atmospheric oxidation.In period Ⅱ,the secondary aerosol formation potential was low,with no obvious correlation with the air pollutants.Meanwhile,the aerosol mass decreased,instead of showing a peak,with increasing aging time.Backward trajectory analysis during the two periods confirmed that the air mass in Period Ⅰwas mainly from local sources,while it was attributed mostly to long distance transport in Period Ⅱ.The air lost its reactivity during the long transport and the particles became highly aged,resulting in a low secondary aerosol formation potential.Our experimental results indicated that the in situ measurement of the secondary aerosol formation potential could provide important information for evaluating the contributions of local emission and long distance transport to the aerosol pollution.
