南半球海洋大气气溶胶单颗粒的理化特性分析

运用透射电子显微镜-X射线能谱技术分析了中国第29次南极科考期间采集的大气气溶胶单颗粒样品,获得颗粒物的形貌特征、混合状态、成分组成及数量分布等信息.结果表明,航渡区域海洋上空的颗粒物主要表现为4类:海盐颗粒、矿物颗粒、富硫颗粒和含碳颗粒,其中海盐颗粒占主导,本研究将海盐颗粒又分为新鲜、部分老化及完全老化的海盐颗粒.部分和完全老化的海盐颗粒占海盐颗粒总数的86%,且部分老化的海盐颗粒表面及完全老化的海盐颗粒以长条状Na2SO4成分为主.同时,发现两处采样点(印度洋中东部和南极内陆)的样品中富硫颗粒较多,根据后向气团轨迹判断这些富硫颗粒主要来源于海洋地区,推测是由海洋表面浮游生物释放的二甲基硫(dimethyl sulfide,DMS)经过大气氧化形成.本研究表明,南半球海洋大气中海盐颗粒老化是由海洋表面释放的DMS控制,这不同于北半球海洋大气中人为源影响的海盐颗粒老化现象.     

南北极大气气溶胶单颗粒成分特点研究

运用定量电子探针微区分析技术(EPMA)分别测定了采自北极新奥尔松地区(78?55′N、11?56′E)和南极乔治王岛(62?13′S、58?47′W)极昼天气下PM10大气颗粒物样品.结果表明,北极和南极大气颗粒物化学成分存在很大差异,表现出各自不同的特点.北极的颗粒类型中,“反应的海盐”和“矿物尘”分别占颗粒总数的44%和27%,“新鲜海盐”所占的比例不到10%,“反应的海盐”中以含硝酸盐的颗粒为主,反映了外来物质或人为污染对该地气溶胶影响较大;南极的颗粒类型中,“新鲜海盐”占总数的74%左右,“反应的海盐”占19%,反应的海盐全部含硫酸盐、未发现含硝酸盐的颗粒,推测与海盐反应的含硫物质来源于海洋浮游生物代谢过程产生的二甲硫醚(DMS)及其降解产物,而与人为污染无关.     

西太平洋上空气溶胶的来源及其化学特征的研究

报道了西太平洋海域上空气溶胶的变化情况.尘土粒子的输入量控制着海洋上空气溶胶中元素Al、Fe、Sc、Mn、Co、La、Ce、Eu、Hf、Ta及Th的浓度.相对于海洋和地壳来源的异常富集元素在西太平洋上空气溶胶中富集程度很高.在开阔海域大气中的海盐元素浓度受海盐气溶胶粒子的量所控制,而其它元素则受来自陆地的地壳风化物影响.由于环境污染物的输入.使开阔海域大气的化学组成发生了变化.     

北京市不同天气条件下单颗粒形貌及元素组成特征

使用透射电镜(TEM)对采自北京市2011年3~4月间不同天气条件下的气溶胶样品进行观察,并对比2010年3月沙尘天气和2010年11月18日雾天样品,对可吸入颗粒物PM10的基本形貌、矿物元素组成和硫化特征等做比较分析.结果表明,采样期间PM10主要包括烟尘集合体、飞灰、矿物颗粒、二次反应颗粒等,不同天气条件下颗粒类型并无明显差别.采样期间矿物颗粒以“富Si”颗粒(占总量46%)为主,“富Ca”(总量17%)、“富S”颗粒(总量13%)为次要,“富Fe”(总量7%)及较少“富Na” 颗粒(总量6%)和其他颗粒.沙尘天气中沙尘暴输入大量沙尘颗粒使占颗粒83% 的“富Si”颗粒含量明显高于阴天的36%和雾天的32%.仅在阴天和雾天发现大量“富S”颗粒,其中雾天26%,阴天10.7%,说明这2种天气二次反应强烈,易于生成富S二次颗粒,对颗粒物元素组成产生影响.对所有含S颗粒分析表明,不同天气含S矿物含量差异较大,阴天16%,雾天36%,晴天和沙尘天气则含量很低,说明一定的SO2浓度下,大气湿度越大,硫化现象越明显.雾天颗粒物表面的硫化现象相当严重,在含硫量较高的颗粒中,绝大部分同时含有Ca、Na、Si、Fe等元素,说明大气中含Ca、Na、Si、Fe的碱性矿物对雾水酸性有一定的缓冲作用.     

青岛沿海大气气溶胶中海盐源的贡献

重点研究青岛沿海地区大气气溶胶的海盐来源 .在 Na主要来自于海盐 ,Cl存在亏损的情况下 ,为确定大气气溶胶中的海盐源贡献率 ,将 Na和 Cl作为海盐源参比元素计算得到的海盐源贡献率分别作为上限和下限 ,得出青岛沿海地区大气气溶胶中海盐源的年均质量浓度贡献率大致为 6.3%～ 9.7%.海盐源对气溶胶的贡献随气溶胶粒径增大而增加 .青岛沿海大气气溶胶氯亏损在 36.2 %～ 65.9%范围内 ,是大气中气态无机氯的来源之一 .     

桂林市细颗粒物典型排放源单颗粒质谱特征研究

利用单颗粒气溶胶飞行时间质谱仪(SPAMS)对桂林市四类PM2.5典型污染源排放颗粒物的粒径和化学成分进行分析,结果表明:除扬尘颗粒外,其他几类源排放颗粒物的粒径集中在0.2~1.25μm之间.几类污染源排放颗粒物的化学成分有明显区别,柴油车以EC颗粒为主,占总电离颗粒的74.7%,汽油车以富钙颗粒为主,占总电离颗粒的86.7%,燃煤排放以富铁、富铬颗粒为主,二者合计占了总电离颗粒的59.9%,生物质燃烧以含左旋葡聚糖颗粒为主,占总电离颗粒的44.4%,扬尘颗粒以富铝颗粒为主,占总电离颗粒的69.4%.这些特征为大气颗粒物的源解析提供了可能.     

基于TEM-EDS对四川盆地大气单颗粒气溶胶的研究

为了解四川盆地大气中单颗粒气溶胶理化特征,分别在该区域典型城市（成都市）和背景地区（峨眉山）进行了大气单颗粒样品采集.基于带能谱的透射电子显微镜（TEM-EDS）对两地累计3923个单颗粒的化学组成、形貌特征及混合状态等进行了全面观测和分析,并对两地颗粒物差异性进行了对比分析.结果发现：两地气溶胶颗粒主要包括有机物、富硫、矿物、烟尘和飞灰/金属颗粒,除了以单独的外混形式存在外,大多数颗粒以两种及两种以上颗粒类型混合（即内混）形式存在.通过对成都市不同污染状况下单颗粒特征对比发现,"污染天"的内混颗粒占比高于"清洁天",分别为74.2%和68.6%;相比"清洁天","污染天"颗粒物粒径分布范围更广且峰值区间更大,表明污染过程中颗粒物的大气混合趋于更强.对比成都市与峨眉山分析结果得知,成都市以内混的有机物-硫颗粒为主导（占比为50.2%）,而峨眉山以外混的有机物颗粒为主导（占比为50.5%）;成都市含硫类颗粒物（如有机物-硫颗粒）贡献高于峨眉山,而峨眉山两种含碳类颗粒（如烟尘和有机物-烟尘颗粒）占比高于成都市;此外,成都市与峨眉山两地大气颗粒物粒径分布范围及峰值区间均存在一定差异,进一步体现了两地颗粒物来源和老化混合的差异.在峨眉山,与非降雨天相比,一些易溶于水的颗粒物（如含硫类颗粒）在降雨天占比明显降低,而源自当地燃烧过程、粒径较小且疏水性强的颗粒物（如烟尘和有机物-烟尘颗粒）占比相应升高.     

江浙沪春节燃放烟花爆竹对垂直大气的影响

基于美国宇航局(NASA)的CALIPSO星载激光雷达L1卫星监测数据,通过分析532 nm总后向散射系数、体积退偏比和色比,对江浙沪地区2009—2014年春节期间大气气溶胶光学与微物理特性进行研究,揭示了江浙沪地区春节期间大气气溶胶散射强度、颗粒规则性与颗粒大小的垂直分布特征.结果表明,燃放烟花爆竹产生的颗粒物主要聚集于对流层中低空,使低层大气散射能力增强、颗粒物尺度增大,使对流层中层大气颗粒物不规则性增强;气溶胶散射能力随高度增大单调减弱,不规则气溶胶在6~8 km高度内占比最大,颗粒随高度增大单调减小;对比各年情况发现,散射能力逐年增强.     

内陆输送过程中沙尘单颗粒类型及其非均相反应

采用单颗粒分析方法对2004 年2~3 月发生在北京的3 次沙尘暴的样品中沙尘颗粒物的化学成分进行了测定.3 次沙尘暴的反向轨迹图显示,它们主要来自于中国北部、西北部和蒙古的戈壁沙漠地区,且这些沙尘颗粒主要通过高空长距离输送到下游区域.使用带能谱的扫描电镜对481 个沙尘颗粒进行分析,并根据成分特征,把这些沙尘颗粒划分为8 种类型,主要类型有“富Si”、“富Ca”、“富S”、“富Fe”.将北京样品分析结果与呼和浩特、塔克拉玛干和敦煌的结果进行对比,结果显示,长距离输送的沙尘颗粒表面发生了SO₂ 的非均相化学反应,导致部分颗粒局部的表面发生化学修改作用,且“富Ca”的碱性矿物为非均相化学反应提供了更有利的反应界面.     

雾过程对北京市大气颗粒物理化特征的影响

为了解北京市雾中发生的气溶胶物理化学过程,分别在雾和非雾期间采集了大气颗粒物样品,并使用扫描电子显微镜和x-射线能谱仪分析了所采集的大气颗粒物的微观形貌、粒度分布和化学组成.晴天低污染期间采集的样品中单个颗粒物主要由一次排放的碳粒聚集体和球形飞灰组成;沙尘期间主要由矿物颗粒和碳粒聚集体组成;而在雾期间则出现了大量的由液相反应生成的长条状Ca-K-S颗粒以及主要由硫酸盐所组成的似圆状颗粒.本研究中,雾期间大气中0.2 μm以上颗粒物的数浓度较晴天低污染期间高5～8倍.此外,非雾期间大气颗粒物数浓度随着粒度的增加而降低,而雾期间则在0.4μm附近出现了新模态.结果表明,雾中活跃的大气非均相反应极大地改变了颗粒物的形貌、化学组成、粒度分布等特性.     

内蒙古乌达-乌斯太工业园环境单颗粒研究

2015年夏季在内蒙古乌达-乌斯太工业园布点采集了大气颗粒物核孔膜样品16件,采用扫描电镜（SEM-EDX）共表征了1600个单颗粒的形貌和化学组成,结果表明,研究区单颗粒主要为矿物颗粒、燃烧产生颗粒和含硫颗粒3大类,其中矿物颗粒不仅含有硅铝酸盐和碳酸盐这类常见颗粒,还有风化煤矸石和沙尘颗粒这两种特殊颗粒;燃烧产生颗粒不仅有通常的燃煤飞灰、烟尘集合体和絮状碳质颗粒,还有原煤尘颗粒.统计表明,烟尘聚合体、硅铝酸盐和沙尘这三者占颗粒物总数的64%,风化煤矸石尘和原煤尘主要呈现为可吸入颗粒（2.5~10μm）;烟尘聚合体和沙尘则主要为超细颗粒（<1.0μm）.总之,单颗粒分析揭示该典型煤炭工业园区大气颗粒物主要来源：园内燃煤排放和交通,上风向矿区煤炭生产和上风向沙漠自然活动.     

Atmospheric trace elements over source regions for Chinese dust: concentrations,sources and atmospheric deposition on the Loess plateau

The mass-particle size distributions of up to 17 trace elements in aerosol particle samples from dust storm and non-dust storm periods were determined for three sites in or near the source regions of Chinese dust. The mass of particulate material in the atmosphere at the sites is dominated by mineral aerosol particles. An absolute principal component analysis of the non-dust storm elemental data for the loess region allows the estimation of the mass contributions from two coarse-particle classes (soil dust and dust associated with pollutants), and two fine-particle classes (soil dust and anomalously enriched). For most elements (Al, Si, Ca, Fe, Ti, K, S and As), the mass-particle size distributions (MSDs) were approximately log-normal. The mass-median diameters (MMDs) of the soil-derived elements tended to decrease with distance from the desert region and when the dust storms subsided. Total dry deposition velocities were calculated by fitting a log-normal distribution to the aerosol data and calculating deposition rates for 100 particle-size intervals using a two-layer deposition model. The mean dry-deposition rates and fluxes were highest during dust storms over desert regions. In thloess region, the calculated dry deposition velocities of soil derived elements (Al, Si, Ca, Fe and Ti) during non-dust storm periods were from 3.1 to 3.7 cm s⁻¹. From the estimated mass-particles size distributions, the coarser and finer mineral particles were found to benriched with Ca, Fe, Ti and K relative to Al or Si. On a yearly basis, the dry atmospheric input to the Loess Plateau was mainly attributable to normal transport processes, i.e. non-dust storm conditions. Wet deposition fluxes estimated from scavenging ratios indicate that dry deposition dominated the total atmospheric deposition of mineral aerosol. The deposition of aerosol particles associated with coal burning or other anthropogenic sources also was considerable on the Loess Plateau.     

运用单颗粒气溶胶质谱技术初步研究广州大气矿尘污染

自主研发的单颗粒气溶胶飞行时间质谱仪(Single Particle Aerosol Mass Spectrometer,SPAMS)采用空气动力学透镜、双激光测径系统以及双极飞行时间质量分析器,并用其对广州市大气细颗粒物进行在线分析,实现了矿尘颗粒物的空气动力学直径和化学组成的同时检测. 在连续4 d的采样中,共采集到249 057个粒径在0.2～1.2 μm且同时含有正负质谱信息的颗粒物,其中矿尘颗粒物占7.9%. 结果表明:矿尘颗粒物的正离子成分以Ca2+,K+>/sup>,Fe2+和Na+>/sup>为主,同时还含有Li+>/sup>,Mg2+,V>/sup>5+,Ba2+和Ti4+等;负离子成分以NO₃->/sup> 和NO₂->/sup>为主,另外还含有HSO₄->/sup>,SiO₃->/sup>和PO₃->/sup>等. 在广州市大气细颗粒物中,矿尘贡献不如含碳颗粒物和生物质燃烧颗粒物,且在矿尘颗粒物中贡献较大的几类(如含钙、含铁、含钠钾颗粒物等)大多是老化的成分.      

Aerosol-soil fractionation for Namib Desert samples

Four soil samples, collected in the central Namib Desert, were fractionated by dry sieving and aerosol generation into 16 size fractions in the range 0.15–300 μm diameter. The mass-size function of each soil and the dust (mineral aerosol) generated from the soil were studied. Due to the preferential lifting of smaller soil particles by the air stream, the soil underwent strong physical fractionation resulting in the bulk of the dust being found in the range of 1.3–10.3 μm, whereas the bulk of the soil was found in the range 63–300 μm. The concentrations of 11 elements in eight soil size fractions (from <45 to >300 μm) obtained by dry sieving were measured by X-ray fluorescence analysis while the concentration for these elements in eight size ranges (from <0.15 to >10.3 μm) obtained by aerosol generation were determined by particle-induced X-ray emission. The concentrations of the elements Al, Si, K, Rb and Sr were found to vary by less than a factor of two throughout the particle size range studied. However, the concentration of the elements Ca, Ti, Mn, Fe, Y and Zr increased when the particle size decreased below 150 μm to reach a maximum around 63-45 μm and then to decrease. The concentrations of the elements in the generated aerosol particles were found to be more similar to those in the bulk soil than any particular size fraction. For the aerosol size fraction, elemental enrichment factors were calculated with respect to the composition of average crustal rock, average soil, the bulk Namib soil and the small size fraction of the Namib soil. For several elements, the enrichment factors varied quite significantly, depending on the choice of the reference material. The elemental ratios in the mineral aerosol were also compared to those in the atmospheric aerosol from the Namib Desert. It was confirmed that there is a marine contribution for S, Cl and Sr in the Namib natural aerosol. The composition of the mineral aerosol generated in this study should be useful in source apportionment studies for the Namib Desert and sorrounding regions.     

Nitrate formation on sea-salt and mineral particles—A single particle approach

Heterogeneous reactions of NO₂ and HNO₃ at sub-ppm levels with individual sea-salt and mineral particles were investigated. Particles deposited on filters and on electron microscope grids placed in a Teflon reaction chamber, were exposed to NO₂ or HNO₃ under controlled conditions. Experiments were carried out under dark conditions and were repeated under u.v. radiation (solar simulation). Nitrates formed on the particles were determined by bulk and individual particle analyses. Individual sea-salt and mineral particles were observed in a transmission electron microscope for the presence of nitrate on the particle surface.The formation of nitrates on sea-salt particles under dark conditions, was in the range of 0.1–3.3 mg NO₃⁻ g⁻¹ NaCl. Higher values were obtained for mineral particles: 0.2–8.2 mg NO₃⁻ g⁻¹ aerosol ([NO₂] =0.18 and 0.54 ppm; [HNO₃] = 0.04 ppm; exposure time 1–7 days; relative humidity = 70%). The formation of nitrates on sea-salt particles increased from 3.0 to 16.1 mg NO₃⁻ g⁻ NaCl when u.v. radiation was added. Mineral particles did not show a significant increase in nitrate formation under u.v. radiation.Microscopy showed that about 50% of the soil particles reacted with NO₂ and HNO₃ to form mixed nitrate particles. Almost all sea-salt particles (above 95%) reacted with both gases, although the reaction was not complete and took place only on the particle surface.Application of electron microscopy and a specific microspot technique provided direct evidence for the formation of nitrate on sea-salt and mineral particles exposed to NO₂ and HNO₃.     

Size, composition, and mixing state of individual aerosol particles in a South China coastal city

Aerosol samples were collected in summer in Macao,a coastal city of the Pearl River Delta Region in China.Morphology,size,elemental composition,and mixing state of individual aerosol particles were determined by scanning electron microscopy coupled energy dispersive X-ray(SEM/EDX) and transmission electron microscopy(TEM).Based on the morphologies of 5711 aerosol particles,they consist of soot(32%),mineral(17%),secondary(22%),and unknown fine particles(29%).The sizes of these particles were mostly distributed between 0.1 and 0.4 μm.Compositions of 202 mineral particles were obtained by SEM/EDX.Mineral particles were mainly classified into three types:Si-rich,Ca-rich,and Na-rich.The compositions of typical mineral particles can indicate their sources in sampling location.For example,mineral particles,collected along the main street,were associated with trace amounts of heavy metals,such as Zn,Ti,Mn,Ba,Pb,and As.TEM observations indicate that most Na-rich particles were aged sea salt particles(e.g.,Na2SO4 and NaNO3) which formed through heterogeneous chemical reactions between sea salt and acidic gases.Additionally,aging time of soot was short in Macao due to high humidity,high temperature,and high levels of sunlight in Macao.Most of soot and fine mineral dust particles were internally mixed with secondary particles.     

新疆阿克达拉大气背景点气溶胶物质来源研究

文章利用2004年7月~2005年3月间新疆阿克达拉区域大气本底观测站PM10和TSP有机碳、元素碳及水溶性离子的组成数据,分别采用主成分分析法(Principal Component Analysis,PCA)和绝对主成分分析法(Absolutely Principal Component Analysis,APCA)对大气气溶胶物质来源进行研究。结果表明PM10中气溶胶来源及贡献率分别为:人为污染源(49.6%)、地壳矿物质粉尘(17.3%)、盐渍化地壳矿物质粉尘(33.1%);TSP中气溶胶来源及贡献率分别为:盐渍化地壳矿物质粉尘(21.3%)、地壳矿物质粉尘及人为污染混合源(50.8%)、人为污染源(27.8%)。由于阿克达拉大气本底观测站位于我国气候上游,该站PM10和TSP中不同来源物质贡献率的源解析结果对于研究中国西北地区大气背景气溶胶的特性及其气候效应具有重要意义,对我国西北边境大气背景区空气污染治理对策的制定有一定的参考价值。     

Aerosols in Santiago de Chile: A study using receptor modeling with X-ray fluorescence and single particle analysis

Between 15 January and 26 February 1987, 51 fine and coarse mode aerosol samples were collected at the Universidad de Santiago de Chile Planetarium using a dichotomous sampler. The samples were analyzed by X-ray fluorescence for up to 17 elements (Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb). Aerosol particles were individually studied by Electron Probe Microanalysis (EPMA) and Laser Microprobe Mass Analysis (LAMMA). The data set consisting of aerosol elemental concentrations and meteorological variables was subjected to Principal Factor Analysis (PFA), allowing the identification of six fine mode particle source classes (soil, industrial, sulfate particles, traffic, residual oil, wood-burnings), and five coarse mode particle source classes (soil, industrial, traffic, residual oil, sulfate particles). Both PFA solutions explained about 81 and 90% of the total variance in the data set, respectively. The regression of elemental mass concentrations on the Absolute Principal Factor Scores allowed the estimation of the contribution of the different source classes to the Santiago aerosol. Within the fine fraction, secondary SO₄²⁻ particles were responsible for about 49% of the fine mode aerosol mass concentration, while 26, 13, 6.4 and 5.6% were attributed to wood-burning/car exhausts, residual oil combustion, soil dust/metallurgical, and soil dust/wood-burning releases, respectively. The coarse fraction source apportionment was mainly dominated by soil dust, accounting for 74% of the coarse mode aerosol mass concentration. A composite of soil dust and industrial release accounted for 13%; a composite of secondary sulfates contributed with 9%; a composite of soil dust and automotive emissions, and secondary sulfates were responsible for 4 and 0.03% of the coarse aerosol mass concentration, respectively. EPMA results are in satisfactory agreement with those from the bulk analysis and allowed the identification of eight particle types in both fine and coarse mode aerosols, pertaining to different source classes, namely soil, seaspray, secondary SO₄²⁻, metallurgical emissions and biomass burning release. EPMA also evidenced that one of the most abundant particle types corresponded to marine aerosol, having an average diameter of 0.7 μm for the fine mode and 2.2 μm for the coarse mode aerosol. LAMMA results indicate that, in fact, seaspray has been transported into the city of Santiago de Chile airshed, suffering several transformations and a sulfur enrichment. This analytical technique also provided evidence of the abundance of carbon-rich particles, which were not detected by either the bulk X-ray analysis or EPMA; they are probably due to fossil-fuel combustion releases.     

太原市冬季大气气溶胶的源识别

用可对气溶胶粒径切割的采样器采集了太原市中心1985年冬季的大气气溶胶样品。以X射线荧光法分析出的化学元素作为变量,对数据作了因子分析、标示元素多元回归处理。结果指出,粒径小于2.5μm的细粒子中约有76.5％来自燃煤排放出的SO2转化成硫酸盐,约13.5％来自建筑石料高温烧结;2.5—15μm之间的粗粒子中约有82.8％来自燃煤排放出的煤飞灰;在TSP范围内,混合尘与燃煤两类源的贡献率分别是41.6％和45.2％。源识别结果表明太原市冬季气溶胶主要来自煤炭燃烧,而石油化工、金属冶炼及汽车尾气等源的贡献很小。工业粉尘、基建扬尘、路面及自然风沙等类型的源,主要在大粒径范围内（TSP）才有贡献。 就燃煤源而论,工业用煤对气溶胶（飘尘部分）污染的贡献约是居民用煤的11.8倍,因此,研究解决工业燃煤造成的大气污染是一个主要问题。"