Hygroscopicity of particles generated from photooxidation of α-pinene under diferent oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with diferent sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem diferential 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.     

Hygroscopicity of particles generated from photooxidation of α-pinene under different oxidation conditions in the presence of sulfate seed aerosols

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.     

Water uptake of multicomponent organic mixtures and their influence on hygroscopicity of inorganic salts

The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds(WSOCs) and their effects on ammonium sulfate(AS) and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer(HTDMA) in the relative humidity(RH) range of 5%–90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model(E-AIM) and Zdanovskii–Stokes–Robinson(ZSR) method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles.When organic content was dominant in the mixture(75%), the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles.     

Optical monitoring of particle aggregates

Methods for monitoring particle aggregation are briefly reviewed. Most of the techniques are based on some form of light scattering and may be greatly dependent on the optical properties of aggregates, which are not generally known. As fractal aggregates grow larger their density can become very low and this has important practical consequences for light scattering. For instance, the scattering coe cient may be much less than for solid objects, which means that the aggregates can appear much smaller than their actual size by a light transmission method. Also, for low-density objects, a high proportion of the scattered light energy is within a small angle of the incident beam, which may also be relevant for measurements with aggregates. Using the “turbidity fluctuation” technique as an example, it is shown how the apparent size of hydroxide flocs depends mainly on the included impurity particles, rather than the hydroxide precipitate itself. Results using clay suspensions with hydrolyzing coagulants and polymeric flocculants under di erent string conditions are discussed.     

Investigating the effect of volatility on the hygroscopicities of acetate nanoparticle aerosols by surface plasmon resonance microscopy

Under high relative humidity(RH) conditions, the release of volatile components(such as acetate) has a significant impact on the aerosol hygroscopicity. In this work, one surface plasmon resonance microscopy(SPRM) measurement system was introduced to determine the hygroscopic growth factors(GFs) of three acetate aerosols separately or mixed with glucose at different RHs. For Ca(CH₃COO)₂ or Mg(CH₃COO)₂ aerosols, the hygroscopic growth trend of each time...     

Evolution in physiochemical and cloud condensation nuclei activation properties of crop residue burning particles during photochemical aging

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.     

Characteristics of nanoparticles emitted from burning of biomass fuels

The characteristics of the particles of the smoke that is emitted from the burning ofbiomass fuels were experimentally investigated using a laboratory-scale tube furnace and different types of biomass fuels： rubber wood, whole wood pellets and rice husks. Emitted amounts of particles, particle-bound polycyclic aromatic hydrocarbons （PAHs） and water-soluble organic carbon （WSOC） are discussed relative to the size of the emitted particles, ranging to as small as nano-size （〈70 nm）, and to the rate of heating rate during combustion, differential thermal analysis （DTA） and thermogravimetric analysis （TG） techniques were used to examine the effect of heating rate and biomass type on combustion behaviors relative to the characteristics of particle emissions. In the present study, more than 30% of the smoke particles from the burning ofbiomass fuel had a mass that fell within a range of 〈 100 nm. Particles smaller than 0.43 μm contributed greatly to the total levels of toxic PAHs and WSOC. The properties of these particles were influenced by the fuel component, the combustion conditions, and the particle size. Although TC--DTA results indicated that the heating rate in a range of 10-20℃did not show a significant effect on the combustion properties, there was a slight increase in the decomposition temperature as heating rate was increased. The nano-size particles had the smallest fraction of particle mass and particle-bound PAHs, but nonetheless these particles registered the largest fraction of particle-bound WSOC.     

Hygroscopic properties of sodium and potassium salts as related to saline mineral dusts and sea salt aerosols

Mineral dust, soil, and sea salt aerosols are among the most abundant primary inorganic aerosols in the atmosphere, and their hygroscopicity affects the hydrological cycle and global climate. We investigated the hygroscopic behaviors of six Na- and K-containing salts commonly found in those primary organic aerosols. Their hygroscopic growths as a function of relative humidity (RH) agree well with thermodynamic model prediction. Temperature dependence of deliquescence RH (DRH) values for five of those salts was also investigated, which are comparable to those in literature within 1%–2% RH, most showing negative dependence on temperature. Hygroscopic growth curves of real-world soil and sea salt samples were also measured. The hygroscopic growths of two more-hydroscopic saline soil samples and of sea salt can be predicted by the thermodynamic model based on the measured water-soluble ionic composition. The substantial amounts of water-soluble ions, including Na⁺ and K⁺, in saline soil samples imply that even nascent saline soil samples are quite hygroscopic at high-RH (>80%) conditions. For three less-hygroscopic dust samples, however, measurements showed higher water uptake ability than that predicted by the thermodynamic model. The small amount of water taken up by less-hygroscopic dust samples suggests that dust particles might contain thin layers of water even to very low RH. The results of this study provide a comprehensive characterization of the hygroscopicity of Na- and K-containing salts as related to their roles in the hygroscopic behaviors of saline mineral dusts and sea salt aerosols.     

Numerical simulation of the sedimentation of cylindrical pollutant particles in fluid

The sedimentation of cylindrical pollutant particles which fall through a fluid is investigated. Differing from previous research work,particle oscillation and effect of particle on the fluid are considered, and the torque exerted on a particle when viscous fluid flow around a particle is got through experiment and included in the numerical simulation. The computational results showed that the sedimentation velocities of particle increase slowly with the increase of particle aspect ratio 9. For disk-like particle, when the motion direction of particle is parallel to axis of particle, particle falls more slowly than the case of perpendicular to axis of particle; while for rod-like particle, it is inverse. For sedimentation of a crowd of high-frequency oscillating cylindrical particles with arbitrary initial orientation, both vertical velocity and horizontal velocity oscillate dramatically, the degree of oscillation of the former is stronger than the later. A crowd of particles fall more quickly than an isolated particle. Particles tend to strongly align in the direction of gravity. The computational results agreed well with the experimental ones and helpful for controlling of pollutant particles.     

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.     

南京北郊大气气溶胶的吸湿性观测研究

大气气溶胶的吸湿性不仅影响气溶胶的光学特性进而影响大气能见度,并且影响气溶胶的直接和间接气候效应.本文利用加湿串联差分迁移分析仪H-TDMA,于2012年5~7月在南京地区,对40~200nm大气气溶胶粒子在不同相对湿度下的吸湿增长因子进行了观测研究.统计结果表明:在90%相对湿度下,颗粒物的吸湿增长因子GF多为双峰分布,分为GF1.15的强吸湿组分.弱吸湿组分的吸湿增长因子(GFLH)在1.10~1.14之间;对应的强吸湿组分增长因子(GFMH )范围在1.47~1.58之间变化.相同粒径下的离散程度(σ)强吸湿组大于弱吸湿组,说明强吸湿组的粒子化学成分更复杂,异质性更强.相对湿度的变化对粒子吸湿增长的影响与粒子大小及化学组分有关,爱根核模态和积聚模态粒子在相同的相对湿度下潮解点不同,硝酸铵和硫酸铵是颗粒物中的主要吸湿成分.对不同天气条件下的气溶胶吸湿性分析,发现污染期间的吸湿增长因子(GF)和强吸湿组的数目比例(NFMH)都高于清洁期间,这与当时的气象条件以及粒子的内外部混合状态相关.观测还发现气溶胶粒子的吸湿性有明显的日变化特征,白天光照所引发的光化学反应以及混合层演变而造成粒子的吸湿性较强.机动车尾气排放的黑碳等不吸湿或弱吸湿颗粒物也会因为影响颗粒物的化学成分并进而对气溶胶吸湿性产生影响.     

南京冬季云凝结核活化特征及闭合研究

2017年12月~2018年1月在南京地区对气溶胶的云凝结核（CCN）活化特征进行外场观测,并利用4种常用的闭合方法实现对CCN数浓度的预测.结果表明本次观测期间南京地区的气溶胶具有较高的CCN活性,吸湿性参数（κ）的平均值为0.36.对清洁到不同程度雾-霾天气溶胶污染的CCN活化特征进行对比分析,发现随着污染程度的加深,气溶胶的吸湿性逐渐减弱;在同一能见度（VIS）范围内,环境相对湿度（RH）更高的天气类型中气溶胶的吸湿性和活化能力也更高,这可能由于高RH条件能促进大气中非均相及液相反应生成更多的二次无机气溶胶.4种闭合方法的结果显示,利用临界粒径、截断粒径及粒径分辨的活化谱三种方法总体上均有较好的闭合结果.其中,对于低过饱和度（S）下的预测来说,利用截断粒径方法的闭合结果最为理想.     

实验室发生纳米气溶胶吸湿性表征

气溶胶吸湿特性对于灰霾的形成、气溶胶对气候变化的影响及人体健康效应具有重要意义.采用加湿迁移差分分析(HTDMA)法,对实验室发生的8种纳米级无机和有机气溶胶进行吸湿特性定量表征,从而判定影响气溶胶吸湿特性的主要因素.结果表明,NaCl和(NH4)2SO4气溶胶的潮解点为相对湿度(RH)75%±2%,与理论计算结果相接近,说明测试系统具有一定的可靠性.对以往研究较少的NaNO3,CaCl2,CaSO4,合成海盐,乙二酸和己二酸气溶胶的测试表明,NaNO3,CaCl2以及合成海盐气溶胶随RH的升高粒径逐渐增大;合成海盐气溶胶在RH为86%时吸湿性生长因子(Gf)达到1.80;CaSO4,乙二酸和己二酸气溶胶随着RH增大未见明显吸湿增长.通过扫描电镜分析了8种化合物气溶液在不同RH下的形态特征,为掌握各种化学组分对气溶胶吸湿特性的影响提供了微观形态分析的依据.     

鹤山气溶胶光学性质和单颗粒化学组分的研究

2014年10~11月在广东省鹤山大气超级站利用单颗粒气溶胶质谱仪（SPAMS）、积分式浊度仪和黑碳仪在线观测了单颗粒气溶胶的化学组成与气溶胶光学特征.采用Art-2a分类法将单颗粒分为9类：有机碳-硫酸盐/硝酸盐颗粒（OC-Sulfate/Nitrate）、元素碳-硫酸盐/硝酸盐颗粒（EC-Sulfate/Nitrate）、元素碳有机碳-硫酸盐/硝酸盐颗粒（ECOC-Sulfate/Nitrate）、高分子有机碳颗粒（HOC）、海盐颗粒（Sea-salt）、硅酸盐颗粒（Si-rich）、左旋葡聚糖颗粒（Lev）、钾-硫酸盐/硝酸盐颗粒（K-Sulfate/Nitrate）、金属颗粒（Metal）.从清洁期到灰霾期气溶胶的吸收系数、散射系数和单次散射反照率（SSA）显著升高,气溶胶消光能力增强,同时EC-Sulfate/Nitrate颗粒占比从34.8%降至31%,OC-Sulfate/Nitrate颗粒从9.9%增加至23.6%,K-Sulfate/Nitrate二次颗粒从8.5%增加至14%,且灰霾期OC-Sulfate/Nitrate颗粒与硫酸盐、硝酸盐和铵盐的混合程度增强,因此老化的OC-Sulfate/Nitrate颗粒和二次组分颗粒对气溶胶消光系数的增加有重要贡献.在大气相对湿度从50%增加到70%以上的过程中,气溶胶散射系数和吸收系数升高,消光系数由326.1Mm^-1增加到362.9Mm^-1,SSA有所下降,PM_2.5质量消光效率由4.98增加到5.99,EC-Sulfate/Nitrate颗粒和K-Sulfate/Nitrate二次颗粒占比下降,而OC-Sulfate/Nitrate颗粒的占比由7.79%增加到14.29%,且OC-Sulfate/Nitrate颗粒中富含硫酸盐、硝酸盐和铵盐,表明高相对湿度下老化的OC-Sulfate/Nitrate颗粒数目增多对气溶胶消光系数的增强有重要影响.     

成都市冬季相对湿度对颗粒物浓度和大气能见度的影响

利用成都市城区2015年12月的连续在线观测数据,如相对湿度（RH）、能见度、颗粒物（PM₁₀、PM_2.5和PM₁）浓度、气态污染物（SO₂和NO₂）浓度以及PM_2.5中SO₄^2-和NO₃^-浓度,探讨RH对颗粒物浓度和大气能见度的影响.结果表明,高颗粒物浓度和高RH协同作用导致低能见度事件.观测阶段,PM_2.5在PM₁₀中的平均比重为64%,表明成都市冬季细颗粒物污染严重;随着RH增加,PM_2.5/PM₁₀显著增加,表明高RH会加重细颗粒物污染.随着PM_2.5浓度增加,能见度呈幂指数下降;在相同PM_2.5浓度下,RH越高,能见度越低.当颗粒物浓度较低时,RH对能见度的影响作用较强;当颗粒物浓度较高时,大气消光主要由PM_2.5浓度控制,RH对能见度的影响减弱.当RH大于70%时,硫氧化率（SOR）和氮氧化率（NOR）的均值分别从0.27和0.11（RH小于40%）增长至0.40和0.19,表明较高RH对二次硫酸盐和硝酸盐的生成有显著的促进作用,二次硫酸盐和硝酸盐单独或协同影响空气质量.     

Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system

Selective catalytic reduction (SCR) denitration may increase the emission of NH₄⁺ and NH₃. The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization (WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system. The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH₄⁺ will generate new ammonium-containing particles and gaseous ammonia. The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation. Therefore, even if the concentration of NH₄⁺ in the desulfurization slurry is quite low, a high level of NH₄⁺ was still contained in the fine particles at the outlet of the scrubber. When the accumulated NH₄⁺ in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH₃ to NH₄⁺ and increased the additional emission of primary NH₄⁺ aerosols. With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH₄⁺ emitted from entrainment and evaporation of the desulfurization slurry decreased. In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH₄⁺ concentration and pH values of the slurry.     

广州市大气气溶胶散射吸湿增长因子的观测研究

利用环境湿度的日变化,对广州市大气气溶胶散射吸湿增长因子进行了观测研究.基于反向轨迹模型HYSPLIT,将2006年7月到达广州市区的气溶胶分为海洋型、海洋/城市混合型、城市型3个类型.整个观测期间,海洋型、海洋/城市混合型、城市型气溶胶的散射吸湿增长因子f(RH=80%)的平均值分别为2.68±0.59、2.29±0.28、2.04±0.28.经验公式f(RH)=1+a(RH/100)b能够较好地拟合3种类型的气溶胶散射吸湿增长因子,海洋型、海洋城市混合型、城市型气溶胶的散射吸湿增长因子的拟合经验参数a分别为4.92、3.26、2.06,经验参数b分别为5.04、3.85、3.60.     

上海城区二次气溶胶的形成:光化学氧化与液相反应对二次气溶胶形成的影响

二次组分是大气细颗粒物中最重要的组成部分之一.本研究旨在探究上海城区大气气溶胶颗粒物中二次组分的贡献及其形成的主要影响因素.利用高分辨率飞行时间气溶胶质谱仪(HR-TOF-AMS)对上海城区春季及夏季的亚微米颗粒物(PM_1)进行实时的在线表征,发现有机物是PM_1中最主要的组成部分,占比为55%;其次是硫酸盐(24%)与硝酸盐(10%).进一步结合正交矩阵因子解析模型(PMF)对有机组分进行了来源解析.结果表明,一次有机气溶胶(POA)与二次有机气溶胶(SOA)分别占总有机物浓度的34%与66%; POA主要来自机动车源与餐饮源的贡献,且在春季和夏季对有机物的贡献趋于稳定.观测期间共观察到3个二次气溶胶显著生成的过程:其中,春季二次组分的显著增长过程以硫酸盐和老化的有机气溶胶在正午时段上升显著为主要特征,主要受光化学氧化过程的促进;夏季二次组分的显著生成过程主要是液相反应与光化学氧化共同促进的结果,如液相反应过程中,硝酸盐浓度与颗粒相水含量有较好的相关性(R~2=0. 72),而光化学氧化期间SOA浓度与大气氧化性(O_x)有较好的相关性.总体而言,二次组分是上海城市大气气溶胶颗粒物中最重要的组成部分,二次有机与无机组分在PM_1颗粒物中占比分别为35. 5%和43%,光化学氧化与液相反应对二次组分的形成有显著的促进作用.