Composition and temperature dependence of the deliquescence properties of hygroscopic aerosols

Thermodynamic considerations are given to the hygroscopicity of inorganic salts comprising most of the ambient aerosols. Equations are derived expressing the deliquescence humidity as a function of composition and temperature for either single-salt or multicomponent aerosols. Experimental results obtained with charged salt particles individually suspended in an electrodynamic cell are compared both with theory and with available literature data on relative humidities over saturated aqueous solutions. The good agreement found between theory and experimental measurements indicates that aerosol deliquescence properties are predictable from the principle of solution thermodynamics. Furthermore, the experimental technique described here is ideally suited for providing data for complex aerosol systems about which no information is yet available.     

北京大气气溶胶表面无机组分的静态飞行时间二次离子质谱研究

采用特定的样品处理方式,利用静态飞行时间二次离子质谱(Static-TOF-SIMS)技术,对使用通用型大气污染物采样仪VAPS(URG-3000K)采集于非导电性的滤膜(聚碳酸酯滤膜)上的大气气溶胶细粒子(PM_2.5)与粗粒子(PM_2.5～10)的表面无机组分进行了探索性的比较分析.结果表明:大气气溶胶细粒子与粗粒子的表面无机组分组成特征具有明显的差异;气溶胶细粒子表面存在着大气中二次形成的亲水性化合物,会对其表面的疏水性/亲水性特征产生影响,从而影响其大气化学行为;气溶胶粗粒子表面存在氟化物,对生态环境和人体健康具有潜在的危害性,应该重视对气溶胶中氟污染的研究与控制;静态飞行时间二次离子质谱可以成为研究大气气溶胶表面化学组成特征的有利分析手段.      

Analysis of aerosol ammonium nitrate: Departures from equilibrium during SCAQS

The size distribution of the inorganic components of atmospheric aerosols measured during the 1987 Southern California Air Quality Study (SCAQS) are used to investigate the hypothesis that transport limits equilibration of gas- and aerosol-phase ammonium nitrate and influences their size distribution. Estimates of the equilibration time constants at four sites in southern California show a wide range of values; at small values equilibrium is expected whereas at large values departures from equilibrium are expected. An equilibrium indicator is proposed based on the size distributions of aerosol ammonium and nitrate that shows when particles of different size are in mutual equilibrium with respect to ammonium nitrate. Values of the indicator range from unity, demonstrating equilibrium, to less than 0.5, demonstrating that different size particles are not in mutual equilibrium. Comparison of the time constant values to the equilibrium indicator values show a significant correlation, so it is concluded that different size aerosol particles are often not in mutual equilibrium due to transport limitations, supporting the hypothesis. It is concluded that both thermodynamics and mass transport must be considered to predict accurately the size distribution of the volatile inorganics in atmospheric aerosol.     

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.     

Au nanoring arrays as surface enhanced Raman spectroscopy substrate for chemical component study of individual atmospheric aerosol particle

Monolayer-ordered gold nanoring arrays were prepared by ion-sputtering method and used as surface enhanced Raman spectroscopy (SERS) substrates to test the individual atmospheric aerosols particle. Compared to other methods used for testing atmospheric aerosols particles, the collection and subsequent detection in our work is performed directly on the gold nanoring SERS substrate without any treatment of the analyte. The SERS performance can be tuned by changing the depth of the gold nanoring cavity as originating from coupling of dipolar modes at the inner and outer surfaces of the nanorings. The electric field exhibits uniform enhancement and polarization in the ordered Au nanoring substrate, which can improve the accuracy for detecting atmospheric aerosol particles. Combined with Raman mapping, the information about chemical composition of individual atmospheric aerosols particle and distribution of specific components can be presented visually. The results show the potential of SERS in enabling improved analysis of aerosol particle chemical composition, mixing state, and other related physicochemical properties.     

A preliminary analysis of the surface chemistry of atmospheric aerosol particles in a typical urban area of Beijing

Atmospheric aerosol particle samples were collected using an Ambient Eight Stage(Non-Viable) Cascade Impactor Sampler in a typical urban area of Beijing from 27 th Sep.to 5th Oct.,2009.The surface chemistry of these aerosol particles was analyzed using Static Time of Flight-Secondary Ion Mass Spectrometry(Static TOF-SIMS).The factors influencing surface compositions were evaluated in conjunction with the air pollution levels,meteorological factors,and air mass transport for the sampling period.The results show that a variety of organic ion groups and inorganic ions/ion groups were accumulated on the surfaces of aerosol particles in urban areas of Beijing;and hydrophobic organic compounds with short-or middle-chain alkyl as well as hydrophilic secondary inorganic compounds were observed.All these compounds have the potential to affect the atmospheric behavior of urban aerosol particles.PM1.1–2.1and PM3.3–4.7had similar elements on their surfaces,but some molecules and ionic groups demonstrated differences in Time of Flight-Secondary Ion Mass Spectrometry spectra.This suggests that the quantities of elements varied between PM1.1–2.1and PM3.3–4.7.In particular,more intense research efforts into fluoride pollution are required,because the fluorides on aerosol surfaces have the potential to harm human health.The levels of air pollution had the most significant influence on the surface compositions of aerosol particles in our study.Hence,heavier air pollution was associated with more complex surface compositions on aerosol particles.In addition,wind,rainfall,and air masses from the south also greatly influenced the surface compositions of these urban aerosol particles.     

The role of atmospheric aerosol composition in climate change

The chemical composition of atmospheric aerosols has been investigated. Contributions ofsulfate and soot in aerosols to the atmospheric extinction are studied. Discussions are made on the problems of aerosol emitted from volcano, forest fires in northern China, 1987 and oil field fires in Kuwait, 1991. It is indicated that the changes in concentration, particle size, and chemical composition of aerosol after those events could have impacts on the climate change either regionally or globally and that the impact of aerosol particles on climate change could compensate for some temperature increase caused by greenhouse gases and the increase of surface intensity of ultraviolet radiation due to ozone layer depletion.     

免疫进化算法反演均匀混合气溶胶吸湿增长因子

通过对大气消光系数进行组分分解,并借助米散射理论,构建了以均匀混合气溶胶吸湿增长因子为唯一变量的目标函数.进一步利用免疫进化算法优化该目标函数,提出了一种针对均匀混合气溶胶吸湿增长因子的反演算法.基于成都市2017年10~12月浊度计,黑碳仪和GRIMM180环境颗粒物监测仪的地面逐时观测资料以及该时段同时次的环境气象监测数据（大气能见度,相对湿度RH和NO₂质量浓度）,评估了算法的性能及其适用性.结果表明：对所有测试样本而言,反演均匀混合气溶胶吸湿增长因子的免疫进化算法均能快速收敛到全局最优解.建立了成都地区秋冬季均匀混合气溶胶吸湿增长模型,该模型显著提升了环境条件下气溶胶散射系数的模拟精度,其模拟值与实测值之间的平均相对误差仅为12.7%.该反演算法的普适性可为气溶胶吸湿性及其辐射强迫效应的后续研究提供算法保障.     

沙尘暴事件中大气颗粒物化学组分的浓度变化和硫酸盐的形成

应用电感耦合等离子体原子发射光谱、质谱和离子色谱分析了2002年3月28日-4月8日在山东长岛县采集的共11对粗、细大气颗粒物样品的化学组成,探讨4月6-8日沙尘暴事件中大气颗粒物化学组分的变化和硫酸盐的形成.沙尘暴事件应区分前锋和后续部分,前锋与大气中各种污染物相互作用,具有硫富集的特征.后续部分较好地保持了长距离传输风沙尘本身的特征.硫酸盐的形成机理可能是多相氧化而不是简单的酸碱中和.硫酸铵是首先生成的含硫物种,这是细颗粒主导的形成过程.硫酸铵逐渐转化为其他硫酸盐,硫的成分也逐渐向粗颗粒转移.在沙尘暴事件中含硫污染物不但有一个从气相向颗粒物转变的过程,也有一个从细颗粒向粗颗粒转化的过程.      

The distribution of ammonium salts among a size and composition dispersed aerosol

The chemical and physical processes that govern the distribution of ammonium salt condensate over a size- and composition-dispersed aerosol particle population are considered. From an analysis of the concentration profiles of ammonia, nitric acid, and hydrochloric acid vapors surrounding an aerosol particle, the single particle fluxes of these species are derived. By evaluating the time scales for equilibration of the vapor-phase species with a population of aerosol particles, it is found that ammonium salts in the gas and aerosol phases are not always in equilibrium, especially under less polluted and cooler conditions. The principles that govern the distribution of ammonium salts on aerosol particles of different size and composition are identified, and it is found that thermodynamic equilibrium often does not uniquely determine the distribution of ammonium salt condensate. Thus it is concluded that both transport and thermodynamic properties of the aerosol population govern the distribution of ammonium salt condensate.     

天津市春季气溶胶消光特征和辐射效应的数值模拟

根据GRIMM气溶胶粒谱分析仪对粒子数浓度在线观测资料,拟合了天津市春季霾日和非霾日的气溶胶粒子谱分布,结合同期气溶胶样品化学组分分析结果,利用米散射理论计算分析霾日和非霾日气溶胶消光特征.在此基础上,对辐射传输模式LOWTRAN7中气溶胶光学参量进行了修正,利用修正后的模式模拟霾日和非霾日的地面辐射通量密度.结果表明,观测期间非霾日气溶胶消光系数平均为0.253km-1,散射系数平均为0.213km-1.霾日气溶胶消光系数平均为0.767km-1,散射系数平均为0.665km-1.对比模式计算的辐射通量密度与观测值,表明短波辐射模拟效果较好.     

含铁颗粒物的溶解动力学研究进展

气溶胶沉降是开放大洋可溶性铁的主要来源之一,对海洋初级生产力有重要影响.目前气溶胶可溶性铁的沉降通量仍存在很大的不确定性.主要原因包括：（1）不同来源的气溶胶中可溶性铁的含量差异较大;（2）发生在大气传输中的化学反应能够显著影响气溶胶中铁元素的可溶性.本文总结了过去20a国内外关于含铁颗粒物溶解动力学实验室研究的主要结果,以阐明液相反应对铁可溶性的增强作用.归纳了典型含铁颗粒物在质子促进溶解、配体促进溶解及光还原溶解机制作用下的溶解动力学特征,指出pH值、阴离子类型和光照决定了含铁颗粒物的溶解机制,以及铁的存在形式是决定颗粒物中铁潜在可溶性的最主要因素,最后简单展望该领域未来的发展方向.     

珠江三角洲地区大气中的粒子污染

从珠江三角洲地区航测发现,直径小于1μm的气溶胶粒子每毫升可达几万到几十万个,这类小粒子能沉积在肺泡中,对人的健康危害较大,而它们对能见度影响较小。这类细粒子的来源,除排放源以外,气态污染物的转化也是细粒子二次污染的重要来源。野外烟雾箱模拟实验表明,珠江三角洲二氧化硫转化率最高达12.7%/小时,影响SO₂转化的因素是SO₂起始浓度、相对湿度和光照强度。经估算,珠江三角洲地区现有火电站与拟建火电站所排放的SO₂经转化,单是形成的硫酸盐细粒子(≤1μm)污染浓度,约为每毫升几万个,这是一个不容忽视的问题。对广州城市大气污染物有机无机成分的分析表明,就对人体健康而言,广州市气溶胶中有机成分的污染占主导地位。      

氯化钙种子气溶胶对甲苯二次有机气溶胶与氨形成含氮有机物的影响

苯系物光氧化反应形成的二次有机气溶胶(SOA)是大气细粒子的重要组成部分.SOA羧酸和二元醛组分能与氨反应形成有机酸铵和咪唑类含氮有机物,它们能够吸收205 nm和270 nm的紫外辐射,是棕色碳的主要组分.氯化钙等无机种子气溶胶具有较大的比表面积,可为气相羰基化合物和氨提供凝结与反应载体,从而影响含氮有机物的形成.基于此,本文利用烟雾腔研究氯化钙种子气溶胶存在时甲苯SOA与氨的反应,采用紫外-可见分光光度计测量产物溶液在205 nm和270 nm处的吸光度,并定性研究不同浓度、湿度和酸度的氯化钙种子气溶胶对含氮有机物形成的影响.结果表明:氯化钙种子气溶胶能够促进甲苯SOA含氮有机物的形成;含氮有机物的生成浓度随着氯化钙种子气溶胶浓度和pH值的增加而逐渐增大.但当氯化钙种子气溶胶为碱性时,OH~-会与凝结的有机酸发生酸碱中和反应并抑制二元醛化合物水合形成四醇产物,从而不利于含氮有机物的生成;水分子的增加占据了氯化钙种子气溶胶表面的吸附活性位点,氨被吸附和凝结的量减少,从而导致含氮有机物的生成浓度随着相对湿度的增大而降低.本研究可为人为源SOA棕色碳的形成机制和化学组成研究提供实验依据.     

Second organic aerosol formation from the ozonolysis of α-pinene in the presence of dry submicron ammonium sulfate aerosol

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 ...     

Second organic aerosol formation from the ozonolysis of -pinene in the presence of dry submicron ammonium sulfate aerosol

An indoor chamber facility is described for investigation of atmospheric aerosol chemistry. Two sets of α-pinene ozonolysisexperiments were conducted in the presence of dry ammonium sulfate seed particle: ozone limited experiments and α-pinene limitedexperiments. The concentration of gas phase and particle phase species was monitored continuously by on-line instruments andrecorded automatically by data sampling system. The evolution of size distribution was measured by a scanning mobility particlesizer (SMPS), and α-pinene consumed was measured using GC-FID. Secondary organic aerosol (SOA) produced for seed-free systemis 100% organic in content, resulting from a sufficient supersaturation of low volatility organics to produce homogeneous nucleationfollowed by condensation to the aerosol. Secondary organic aerosol produced in seeded system is a mixture of organic and inorganicconstituents, initially forms via condensation onto the inorganic particles, and subsequent growth occurs via absorption into the organicsurface coating the inorganic core. Although the formation process and the size distribution for seed-free system and seeded system isdifferent, the ultimate mass of SOA formed is equal, and SOA yield for the two system located in the same regression line when usingone-product model, suggesting that the presence of dry ammonium sulfate seed has no measurable effect on the total aerosol yield, and the dry seed particle acts solely as a site upon which organic deposition occurs.     

碳质大气颗粒物的扫描质子微探针分析

碳质颗粒物是大气颗粒物的重要组成部分,对全球气候变化、环境质量、人类健康等有重要影响.本研究使用扫描质子微探针对上海两个典型环境监测点的大气颗粒物及7类污染排放源的单颗粒进行了分析.利用微束非卢瑟福弹性背散射谱micro-EBS(non-Rutherford elastic backscattering,EBS)分析了单颗粒中的C含量,发现燃煤烟尘、燃油烟尘、汽车尾气、柴油公交车尾气等污染源中碳质颗粒物占优,而水泥尘、钢铁工业尘、土壤尘中无机颗粒物占优;中心城区的碳质颗粒物占优,而工业区的无机颗粒物占优,单颗粒物的元素分布可以反映颗粒物发生大气化学反应的重要信息,利用微束质子激发X射线荧谱micro-PIXE(particle induced X-ray emission,PIXE)分析得到了大气颗粒物的S、Ca、Fe等元素分布,发现含Ca的碳质颗粒在大气中发生了硫化反应.     

Atmospheric light absorption—A review

The atmosphere interacts both with incoming as well as outgoing light. Two main processes take place: light scattering and light absorption. Whereas light scattering redistributes any ligh energy in the atmosphere, light absorption converts the light energy to internal energy of the absorbing molecules and eventually transfers it to the surrounding gas as heat.Atmospheric gases absorb light in distinct spectral regions usually at more or less broad bands. Best known is the broad absorption of ozone in the far u.v., being essential for the existence of the biological macromolecules on Earth. Gases known as greenhouse gases, e.g. CO₂, CH₄, N₂O and water vapor absorb a wide range of infrared radiation, and thus are responsible for the greenhouse effects. Since the lifetime of these gases (except water vapor) is considerable, their distribution around the globe is fairly homogeneous.The atmospheric aerosol gives the major contribution to the atmospheric light absorption in the visible and near u.v. and near i.r. Graphitic (black) carbon, the main constituent of soot, is almost exclusively responsible for the light absorption of the particles. The light absorption by aerosols is continuous and covers the whole visible spectral range. It only depends slightly on wavelength.The optical properties of elemental carbon are determined by the size of the particles and their complex refractive index. A variety of refractive indices can be found in the literature for elemental carbon, most likely caused by different production and thus composition of the particles. Soot particles are very efficient in attenuating light; for the average size the particles have more than twice the mass extinction coefficient compared to transparent particles such as ammonium sulfate. The light absorption coefficient of a mixture of elemental carbon and transparent materials is higher for internal than for external mixtures. When incorporated into transparent particles, the absorption properties of elemental carbon can be multiplied and the single scattering albedo will decrease in comparison to an external mixture of the same materials.There are different methods to measure the light absorption coefficient of suspended particles. They can be separated in three groups, depending on the effect or methodology they use, but no standard procedure has been adopted so far.Soot is produced by all combusttion processes. Since most fires on Earth are due to humans, then indirectly humans are the major source of light-absorbing aerosol particles. On a global scale black carbon amounts to 1.1–2.5% of the anthropogenic particles and to 0.2–1% of the total emitted particles. The emission factors for elemental carbon are highest for small sources such as diesel motors or fireplaces.The light-absorbing aerosol consists of fine particles, with most particles having diameters less than a few tenths of a micrometer. Particles in the size range of soot particles have an average lifetime of 7 days in the atmosphere, therefore they can be transported over large distances and are also found in remote regions. Since light-absorbing particles have a variety of sources and sinks and they are involved in precipitation cycles, their distribution on the globe is inhomogeneous. Light-absorption coefficients of the atmospheric aerosol reported in the literature differ by more than four orders of magnitudes at different locations, but nevertheless black carbon particles have been found even at very remote areas, such as the South Pole.Although light-absorbing particles are a minority component in the atmospheric aerosol, their effects cannot be neglected: since the mass extinction coefficient of soot is higher by a factor of two to three compared to transparent particles, light-absorbing substances in the atmosphere can cause at some locations up to half of the visibility reduction; light-absorbing substances in the atmosphere can be responsible for the brown appearance of urban hazes and the discoloration of the sky.The light absorption of the atmosphere in the visible (which mainly is due to particulate matter) has to be taken into account when considering radiative properties and climatic consequences. A small temperature increase due to absorption in the visible is to be expected. The value is around a few tenths of a Kelvin, but no general statement on its magnitude is possible, since a large spatial and temporal variation exists and other factors like surface albedo, the optical depth of the aerosol, its incorporation in clouds and humidity growth of the aerosol have to be considered.     

天津城区大气气溶胶复折射指数的反演及消光贡献分析

气溶胶的复折射指数是直接影响其散射特性和吸收特性的基本物理量之一.为深入研究城市大气气溶胶的复折射指数特征,引入一种具有高时间分辨率优点的反演方法来反演气溶胶复折射指数.依据辐射传输理论,将天津大气边界层观测站观测到的高精度散射系数、吸收系数和数浓度谱分布数据利用查表法代入Mie理论气溶胶粒子群消光计算公式,对大气气溶胶复折射指数进行反演.结果表明:①天津城区2011年4月观测地点0.55 μm波长处的气溶胶复折射指数实部平均值为1.64,虚部平均值为0.015.②气溶胶复折射指数实部和虚部均有明显日变化规律,实部和虚部均与相对湿度呈正相关,与风速呈负相关.③利用反演得到的复折射指数对不同粒径大气气溶胶的消光特性进行计算发现,对散射特性而言,>0.25~1.00 μm粒子对散射系数的贡献率达86%;对吸收特性而言,>0.25~2.50 μm粒子对吸收系数的贡献率为53%,>2.50~32.00 μm粒子对吸收系数的贡献率为47%.研究显示,>0.25~1.00和>1.00~32.00 μm的粒子对吸收系数的贡献率均较高,但对散射系数而言,>0.25~1.00 μm的粒子贡献率较高,因此综合考虑气溶胶散射系数、吸收系数和消光系数,控制>0.25~1.00 μm的气溶胶粒子数浓度可有效改善大气能见度.