乌鲁木齐冬季雾天可吸入颗粒物透射电子显微镜研究

利用透射电子显微镜(TEM)对乌鲁木齐冬季雾天采集的可吸入颗粒物(PM_2.5、PM_2.5~10)的形貌特征和集聚状态进行分析。将乌鲁木齐大气可吸入颗粒物分为烟尘集合体、飞灰、矿物颗粒、硫酸盐和有机颗粒等5种单颗粒类型,并讨论了其来源。TEM分析表明,PM_2.5中烟尘集合体占14%,飞灰占7.4%,矿物颗粒占24%,硫酸盐占16.7%,有机颗粒占20.4%;PM_2.5~10 中烟尘集合体没有观察到,飞灰占4.9%,矿物颗粒占26.8%,硫酸盐占12.2%,有机颗粒占58.5%。     

北京地区PM10与秸秆燃烧排放单颗粒对比分析

采用场发射带能谱扫描电镜(FESEM/EDS)法分析北京怀柔地区PM₁₀与秸秆燃烧排放颗粒的形貌特征和成分差异。结果显示:秸秆燃烧后排放颗粒物多为大粒径颗粒,成分上都含S、Cl和K元素。含有生物质燃烧标志元素K的PM₁₀颗粒物多为含Si、Al和Na元素的燃煤飞灰和矿物颗粒,与秸秆燃烧排放颗粒组成化学元素差异明显。据此推断,北京区域PM₁₀受秸秆燃烧排放影响相对较弱,化石燃料燃烧来源影响仍然显著。     

北京西北城区春季PM10单颗粒形貌类型及成分特征

主要对北京西北城区2010年度春季大气可吸入颗粒物的理化特征进行分析研究,通过利用高分辨率场发射扫描电镜和图像分析技术研究了区内可吸入颗粒物的微观形貌类型及百分含量特征,利用扫描电镜及能谱分析研究矿物颗粒的元素组成及富集类型。结果表明,在西北城区春季大气PM₁₀中可识别出烟尘集合体、球形颗粒、矿物和其他未知颗粒等4种单颗粒类型,沙尘暴天气对矿物颗粒的数量比例影响较大,同时影响颗粒物粒度分布。矿物颗粒按成分可分为"富Si"、"富Ca"、"富Fe"、"富S"、"富Na"、"富Ti"、"富Al"、"富Cl"和"富Mg"颗粒九大类,沙尘天气与非沙尘天气的矿物颗粒均以"富Si"颗粒、"富Ca"颗粒、"富Fe"颗粒、"富S"颗粒等为主。     

西安城北地区秋季PM_(2.5)中的矿尘颗粒污染特征

采用单颗粒气溶胶飞行时间质谱仪(Single Particle Aerosol Mass Spectrometer,SPAMS)对西安市大气矿尘颗粒物进行连续12 d在线分析,共采集到107 425个同时含有正负质谱信息的矿尘颗粒,矿尘颗粒物占PM_(2.5)样本数的8.44%。结果表明,矿尘颗粒物的正离子碎片成分以Na~+、K~+、Al~+、Ca~+、CaO~+、Fe~+为主,同时还含有Pb~+等,负离子碎片成分以NO~-_2和NO~-_3为主,另外还含有HSO~-_4、SiO~-_3、HSiO~-_3、H(NO_3)~-_2等。在西安市大气细颗粒物中,矿尘颗粒物中贡献较大的几类(如含钙、含铁、铁氧颗粒物等)大多是老化的成分。将观测阶段采集到的矿尘颗粒纳入本地污染源谱进行来源分析,其主要来源为扬尘源、工业源、燃煤源和汽车尾气源等。     

Ion chemistry and individual particle analysis of atmospheric aerosols over Mt. Bogda of eastern Tianshan Mountains, Central Asia

Aerosol samples were collected during the scientific expedition to Mt. Bogda in July-August, 2009. The major inorganic ions (Na(?+?), NH??, K(?+?), Mg(2?+?), Ca(2?+?), Cl(?-?), SO2??, and NO??) of the aerosols were determined by ion chromatography. SO2??, NO??, and Ca(2?+?) were the dominate ions, with the mean concentrations of 0.86, 0.56, and 0.28 μg m?3, respectively. These mean ion concentrations were generally comparable with the background conditions in remote site of Xinjiang, while much lower than those in ürümqi. Morphology and elemental compositions of 1,500 particles were determined by field emission scanning electron microscopy equipped with an energy dispersive X-ray spectrometer. Based on the morphology and elemental compositions, particles were classed into four major groups: soot (15.1%), fly ash (4.7%), mineral particles (78.9%), and little other matters (0.8% Fe-rich particles and 0.5% unrecognized particles). Presence of soot and fly ash particles indicated the influence of anthropogenic pollutions, while abundance mineral particles suggested that natural processes were the primary source of aerosols over this region, coinciding with the ionic analysis. Backward air mass trajectory analysis suggested that ürümqi may contribute some anthropogenic pollution to this region, while the arid and semi-arid regions of Central Asia were the primary source.     

Ultrafine particles at workplaces of a primary aluminium smelter

The number concentration and size distribution of ultrafine particles in a S?derberg and a prebake potroom of an aluminium primary smelter have been measured using a scanning mobility particle spectrometer. The particle morphology was studied by transmission electron microscopy (TEM). The study shows the existence of elevated number concentrations of ultrafine particles in both potrooms. The main source of these particles is likely to be the process of anode changing. The ultrafine particles were measured directly at the source but could also be identified as episodes of high number concentrations in the general background air. Unlike the larger particles belonging to the 50-100 nm mode, the nanoparticle mode could not be detected in the TEM indicating that they may not be stable under the applied sampling conditions and/or the high vacuum in the instrument.     

Morphology,microstructure and chemical composition of single inhalable particles in Shanghai,China

The morphology, microstructure, and chemical composition of a variety of particles emitted from coal-fired power plants, steel plants, and vehicle exhausts, which are possible sources of particulate matter (PM) in the atmosphere, were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and compared with particle samples collected from urban atmosphere to identify the best footprint or the suitable indicator relating the existence of studied particles and their possible emitters by the morphology, microstructure, and chemical composition of the particles. The investigation indicated that the particles from these three sources are different in morphology, microstructure, and chemical composition. Sphere aggregates were generally the most abundant components, with silicon and aluminum as major elements. The urban air particulate contained particles similar to those observed in the power plant, steel plant, and vehicle exhaust samples suggesting that all three sources are contributing to the pollution in the city.     

Evaluation of acoustical particle counter for the sizing of fog droplets

An acoustical particle counter (or acoustical particle sizing device) was evaluated for counting and sizing of fog droplets. Fog droplets were generated under controlled conditions in the laboratory. Fog droplet sizes were measured by an optical and an electron microscope and compared to results from the acoustical particle counter. Most of the droplets were found to be in the size range of 5–30 µm. The mean diameters estimated from the acoustical particle counter were in agreement with the microscope values of mean droplet diameter. A Rich 100 condensation nuclei monitor was also operated simultaneously during the fog droplet counting to monitor the condensation nuclei counts in the laboratory. The results indicate that condensation nuclei count is inversely correlated with the fog droplet threshold diameter. Aerosols of uniform size (35 µm) were generated by the vibrating orifice monodisperse aerosol generator and counted at three different flow rates by the acoustical particle counter. The counts/liter/minute were similar, indicating the reliability of the acoustical particle counter.     

Physical characterization,magnetic measurements,REE geochemistry and biomonitoring of dust load accumulated during a protracted winter fog period and their implications

The winter fog in India is a recurrent phenomenon for more than a decade now affecting the entire Himalayan and sub-Himalayan regions covering an area of nearly 500,000 km². Every winter (December–January), the air and surface transports in cities of northern India (Amritsar, New Delhi, Agra, Gwalior, Kanpur, Lucknow, and Allahabad) are severely disrupted with visibility reduced to <50 m at times. Since dust particles are known to act as nuclei for the fog formation, this study is aimed to carry out physicochemical characterization of the dust particulates accumulated during a protracted fog period from one of the severely fog affected cities of north India (Allahabad; 25°27′33.40″N–81°52′45.47″E). The dust-loaded tree leaves belonging to Ficus bengalensis and Ficus religiosa from 50 different locations between January 24 and 31, 2010 are sampled and characterized. The mass of dust, color, grain shape, size, phase constituents, and mineral magnetic parameters, such as magnetic susceptibility, SIRM, χ _fd%, and S-ratio, show minor variation and the regional influence outweighs local anthropogenic contributions. The dust compositions show fractionated rare earth element pattern with a pronounced negative Eu anomaly similar to upper continental crust and further suggesting their derivation from sources located in parts of north and central India.     

Dynamics and origin of PM2.5 during a three-year sampling period in Beijing, China

Systematic sampling and analysis were performed to investigate the dynamics and the origin of suspended particulate matter smaller than 2.5 μm in diameter (PM(2.5)), in Beijing, China from 2005 to 2008. Identifying the source of PM(2.5) was the main goal of this project, which was funded by the German Research Foundation (DFG). The concentrations of 19 elements, black carbon (BC) and the total mass in 158 weekly PM(2.5) samples were measured. The statistical evaluation of the data from factor analysis (FA) identifies four main sources responsible for PM(2.5) in Beijing: (1) a combination of long-range transport geogenic soil particles, geogenic-like particles from construction sites and the anthropogenic emissions from steel factories; (2) road traffic, industry emissions and domestic heating; (3) local re-suspended soil particles; (4) re-suspended particles from refuse disposal/landfills and uncontrolled dumped waste. Special attention has been paid to seven high concentration "episodes", which were further analyzed by FA, enrichment factor analysis (EF), elemental signatures and backward-trajectory analysis. These results suggest that long-range transport soil particles contribute much to the high concentration of PM(2.5) during dust days. This is supported by mineral analysis which showed a clear imprint of component in PM(2.5). Furthermore, the ratios of Mg/Al have been proved to be a good signature to trace back different source areas. The Pb/Ti ratio allows the distinction between periods of predominant anthropogenic and geogenic sources during high concentration episodes. Backward-trajectory analysis clearly shows the origins of these episodes, which partly corroborate the FA and EF results. This study is only a small contribution to the understanding of the meteorological and source driven dynamics of PM(2.5) concentrations.     

Saharan dust contribution to PM₁₀, PM₂.₅ and PM₁ in urban and suburban areas of Rome: a comparison between single-particle SEM-EDS analysis and whole-sample PIXE analysis

From February 15th to April 15th 2009, a period characterised by two episodes of Saharan dust outbreaks in Italy, particulate matter (PM) samples were collected at two stations (urban and suburban) in Rome. Some samples were selected and analysed using the SEM-EDS technique to characterise PM, focussing especially on the mineral contribution. Samples were representative both of days affected by Saharan dust episodes and days without this contribution. Cluster analysis allowed the attribution of each of about 67,000 analysed particles to one of the seven main statistical groups based on their composition. Characteristics of the particulate components identified using SEM-EDS analysis were verified by PIXE analysis carried out on filters collected in a suburban area. Ultimately, the contribution of crustal particles was revealed to be consistently high, highlighting the importance of local and regional mineral contributions, as well as those of Saharan origin. Therefore, quantifying all mineral contributions to resuspended particulate could lead to significant reductions of the PM level also on days not influenced by Saharan dust, thus limiting conditions when PM?? daily limit value (DLV) established by European legislation is exceeded.     

Characteristic, composition, and sources of TSP investigated by HRTEM/EDS and ESEM/EDS

Total suspended particle (TSP) collected at the fifth floor of House Dust in Hunan University, China, was analyzed in terms of microscopic morphology and chemical composition. The fine particles (50?nm-2?μm) in the TSP were analyzed by a high-resolution transmission electron microscope equipped with an energy-dispersive X-ray analyzer (HRTEM/EDS). Results showed that the particles were in shapes of plate, irregular and agglomerate. Based on EDS results, these fine particulate matter was primarily composed of Fe-rich (35.82-61.29%), Ca-rich (30.18-36.77%) and Si-rich (18.95-32.28%) particles. Other elements mainly including Mg (0.47-4.97%), Al (0.45-14.57%), S (0.45-4.73%), K (1.13-2.13%) and Zn (0.67-3.85%) were also observed. The sources analysis indicated that the HRTEM particles mainly originated from coal combustion, traffic emission, vehicles exhaust emission and fugitive soil or cement particulate matter. The coarse particles (4-50?μm) were detected by environmental scanning electron microscopy coupled with energy-dispersive X-ray detector (ESEM/EDS). Based on a simple algorithm, ESEM particles were categorized into five groups: C-bearing (46.15%, 67% and 86.98%), Si + Ca-bearing (21.48?+?11.80%, 16.51?+?10.81% and 16.32?+?10.62%), Si + Al-bearing (20.06?+?12.40%, 20.16?+?11.22% and 15.31?+?11.25%), Si-bearing (34.40%, 26.92% and 27.15%) particles and aggregates, most of which exhibit obvious crystalline structure, and these ESEM particles mainly derived from vehicles exhaust emission, coal combustion, soil, and biomass burning, while the aggregates are indicative of atmospheric reaction progress. HRTEM/EDS and ESEM/EDS are mutual complementary in analyzing the characteristic and determining the sources of TSP.     

A preliminary study on the nature of particulate matters in vehicle fuel wastes

Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and tunneling electron microscopy (TEM) studies of two solid vehicle wastes (pollutants) from petrol- and diesel-fueled engines of Kolkata (India) have detected a significant amount of ultrafine particles in the nanometer scale in these wastes. Both powder XRD and selected area electron diffraction from TEM have confirmed the existence of inhomogeneous distribution of nanocrystallites in these pollutants. Energy dispersive X-ray spectrometry shows that these wastes contain mainly carbon and oxygen as the constituent components. These pollutants are magnetic in nature as seen with SQUID magnetometry, and the presence of a high amount of carbon presumably is likely the origin of the magnetic property.     

奎屯-独山子石化区夏季和秋季PM2.5形貌及矿物组成

PM2.5是城市大气的主要污染物,对人体健康危害巨大。研究PM2.5的形貌特征及矿物组成有助于解析PM2.5的来源和贡献及评估PM2.5对人体健康的风险。利用高分辨率场发射扫描电镜(FESEM)和能谱(SEM-EDX)对以石化为支柱产业的奎屯-独山子石化区域生活区和工业区的夏季、秋季PM2.5的形貌和矿物类型进行了分析。结果表明,奎屯-独山子的PM2.5主要包括矿物颗粒(规则矿物、不规则矿物)、烟尘集合体、球形颗粒(燃煤飞灰和二次粒子)、其他颗粒(生物质、未知颗粒)等4种类型,其中矿物颗粒在数量上和体积上均占优势。夏季规则矿物颗粒较多。从元素组成分析看,夏季PM2.5有"富Si"、"富Al"、"富Fe"、"富Ca"、"富Cu"、"富Zn"等类型,秋季PM2.5有"富Si"、"富Ca"、"富Fe"、"富Zn"、"富Cu"、"富Ti"、"富Ba"等类型,2个季节均以"富Si"颗粒占优势,表明道路扬尘、燃油飞灰、燃煤飞灰、工业粉尘、机动车尾气尘、城市扬尘等污染源是奎屯-独山子石化区夏季和秋季大气污染的主要来源。     

A comprehensive physico-chemical, mineralogical and morphological characterization of Indian mineral wastes

This paper provides a comprehensive characterization of mineral waste such as fly ash, bottom ash, slag and construction demolition (C&D) collected from four different thermal power plants, three steel plants and three C&D waste generation sites in India. To determine utilisation potential and environmental concerns, as received fly ash, bottom ash, slag and C&D waste were analysed for physico-chemical, mineralogical and morphological properties. The physico-chemical properties analysed include pH, moisture content, acid insoluble residue, loss on ignition(LOI), carbon content, fineness, chloride content, sulphate content, reactive silica content, XRF and heavy metal analysis. Morphological and mineralogical characteristics were investigated using scanning electron microscopy–energy dispersive X-ray. Particle size distribution was obtained using particle size analyser. The material analysed has different compositions and were selected with a view to determine their suitability for different applications in cement and concrete industry and for further research studies.     

Aerosol characteristics of different types of episode

Daily and hourly average data from nine air-quality monitoring stations distributed across central Taiwan, which include ten items (i.e., PM₁₀, PM_2.5, wind direction, wind speed, temperature, relative humidity, SO₂, NO₂, NO, and CO), were collected from 2005 to 2009. Four episode types: long-range transport with dust storms (DS), long-range transport with frontal pollution (FP), river dust (RD), and stagnant weather (SW), and one mixed type of episode were identified. Of these four episode types, the SW was the dominant type, averaging about 70 %. The mean ratio of PM_2.5/PM₁₀ was the lowest during the RD episodes (0.42), while the mean ratio of PM_2.5/PM₁₀ was the highest during the SW episodes (0.64). Fine aerosol (PM_2.5) and coarse aerosol (PM_10–2.5) samples were collected by high-volume samplers for chemical composition analysis, from only three stations (Douliou, Lunbei, and Siansi) during the days of SW, RD, DS, and FP. The concentrations of PM_2.5 and three ionic species (NH₄ ⁺, NO₃ ^?, and SO₄ ^2?) all showed significant differences among the four episode types. The highest levels of NO₃ ^? (12.1 μg/m³) and SO₄ ^2? (20.5 μg/m³) were found during the SW and FP episodes, respectively. A comparison on the spatial similarity of aerosol compositions among the episodes and/or non-episodes (control) was characterized by the coefficient of divergence (CD). The results showed higher CD values in PM_10–2.5 than in PM_2.5, and the CD values between RD episodes and the other three episodes were higher than those between two types of episode for the other three episodes. The ratios of SOR (sulfur oxidation ratio), SO₄ ^2?/EC (elemental carbon), NOR (nitrogen oxidation ratio), and NO₃ ^?/EC showed that sulfate formation was most rapid during the FP, while nitrate formation was most rapid during the SW.     

Elemental and individual particle analysis of atmospheric aerosols from high Himalayas

Atmospheric aerosols were collected during the scientific expedition to Mt. Qomolangma (Everest) in May–June, 2005. The elemental concentrations of the aerosols were determined by inductively coupled plasma mass spectrometry. This yielded data for the concentration of 14 elements: Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, and Pb. The mean elemental concentrations were generally comparable with those from central Asia and the Arctic, while much higher than those from Antarctic. Size, morphology, and chemical composition of 900 individual aerosol particles were determined by scanning electron microscopy and energy-dispersive X-ray microanalysis. Based on morphology and elemental composition, the particles were clustered into eight groups: soot (8%), tar ball (3%), alumosilicates/silica (55%), calcium sulfate (16%), Ca/Mg carbonate (2%), Fe/Ti-rich particles (3%), Pb-rich particles (1%), and biological particles (12%). The sampling site, located at 6,520 m in the Himalayas, is particularly remote and located at high altitude. Nonetheless, high aerosol enrichment factors for copper, chromium, lead, nickel, vanadium, and zinc all suggest the influence of long-range transported pollution, while enrichment in calcium and the presence of alumino-silicates in individual particle analyses indicates a distinct mineral dust influence. The backward air mass trajectories showed that the northwestern part of India may contribute to the atmospheric aerosol in the central high Himalayas.     

2008年北京市PM_(10)的粒度分布分形维数变化特征

2007年11月-2008年10月间在北京市市中心和西北城区采集了不同季节的PM10样品,并借助扫描电子显微镜和图像分析软件对其进行粒度分布分形维数分析。结果表明,颗粒物中细颗粒物越多,粒度越细,则颗粒物粒度分布分形维数值越大。2008年西北城区的PM10的粒径分布分形维数较大,市中心的较小。市中心的粒度分布分形维数在1.95～2.59之间,各个季节的分形维数呈现冬季春季夏季秋季,西北城区的粒度分布分形维数在2.58～2.72,各个季节的分形维数呈现秋季夏季冬季春季,说明在市中区冬季PM10粒度较细,而在西北城区秋季的颗粒物偏细。与2005年同季相比,2008年的总体颗粒物和烟尘集合体的粒径分布分形维数较大,矿物颗粒的粒度分布分形维数较小,并且总分布的季节变化一致。2008奥运期间的PM10粒度分布分形维数在2.28～3.39之间变化,标志着颗粒物总体变细的趋势。     

Characterization of individual aerosol particles in workroom air of aluminium smelter potrooms

Aerosol particles with aerodynamic diameters between 0.18 and 10 microm were collected in the workroom air of two aluminium smelter potrooms with different production processes (Soderberg and Prebake processes). Size, morphology and chemical composition of more than 2000 individual particles were determined by high resolution scanning electron microscopy and energy-dispersive X-ray microanalysis. Based on chemical composition and morphology, particles were classified into different groups. Particle groups with a relative abundance above 1%(by number) include aluminium oxides, cryolite, aluminium oxides-cryolite mixtures, soot, silicates and sea salt. In both production halls, mixtures of aluminium oxides and cryolite are the dominant particle group. Many particles have fluoride-containing surface coatings or show agglomerations of nanometer-sized fluoride-containing particles on their surface. The phase composition of approximately 100 particles was studied by transmission electron microscopy. According to selected area electron diffraction, sodium beta-alumina (NaAl(11)O(17)) is the dominant aluminium oxide and cryolite (Na(3)AlF(6)) the only sodium aluminium fluoride present. Implications of our findings for assessment of adverse health effects are discussed.     

Influence of aerosol spectrum and air pollutants on fog formation in urban environment of megacity Delhi, India

Urban areas are facing increasing fog frequencies that may result due to increased air pollution emanating from variety of sources. The increased pollution levels may lead to the atmospheric reactions resulting into the formation of secondary pollutants that may also lead to increased aerosol number concentrations (ANC) in the atmosphere. This could cause enhanced water aerosols in the presence of favourable meteorological conditions and high relative humidity. This study deals with the atmospheric pollution and visibility during winter season of megacity Delhi in order to assess the relationship between the two specifically during fog episodes. Thus, this study analyses the levels of air pollutants, aerosol spectrum and meteorological conditions during one week each in the winter season of the years 2004 and 2006 in order to have an improved understanding of their role in fog formation in mega-city Delhi. More than 300 h of measurements which included episodes of dense, thick and moderate fogs of about 25 h, were studied. The measurements cover most of the accumulation mode and greater size spectrum of aerosols. Thus, the analysis is performed for the entire period, specifically, before the fog sets up, during and afterwards. In general, the relatively small variations in number concentration show larger variations in visibility prior and post dense fog formation than during dense fog episodes. Preliminary analysis of monthly averaged RSPM (Respirable Suspended particulate Matter or PM(10)) concentration values for four winter months for a period of 6 years (1996-2001) and visibility did not show a good correlation with total occurrences of fog. However, daily averaged RSPM concentration showed a good correlation with the occurrences of thick fog. Diurnal variation of Sulfur-dioxide and Nitrogen dioxide were found to have inverse relationship with visibility during fog which may be due to formation of secondary pollutants such as sulfate and to a lesser extent nitrates. Amongst, the daily averaged concentrations of all the criteria pollutants, RSPM was found to be best correlated with the fog in comparison to other pollutants.