Identification and classification of airborne soot particles using an automated SEM/EDX

Individual particle analysis by means of an automated scanning electron microscope with an energy dispersive X-ray microanalysis system (SEM/EDX) is used for chemical classification and size determination of airborne particulate matter. Special attention is paid to the X-ray analysis of atmospheric soot particles. The preparation and use of standards, which is indispensable for obtaining good results are described and discussed in detail. The aerosol samples were collected on Nuclepore filters of two different pore sizes at a traffic island in Munich.     

The elemental composition of breast tissue: Can this be related to breast particle deposition?

In vitro instrumental neutron activation analysis (INAA) has been performed, yielding a range of minor and trace elemental concentrations for 46 paired samples of surgically-excised cancer breast tissue. In addition results of the soft X-ray microradiography of excised breast specimens have been used to quantify breast-particle clustering parameters, including area of cluster and nearest neighbour distance. Significant differences between elemental composition in histologically normal tissues and tissues exhibiting malignant lesions are supported by the observation of significant differences in particle clustering parameters. These observations have led to the investigation of the possible association between elemental composition of diseased breast tissues and the formation of breast particles. In particular a scanning electron microscope (SEM) with an energy dispersive X-ray (EDX) facility has been used to locate breast particles and conduct microanalysis of the particle constiuency. Results indicate these particles to consist of a complex of Ca and other elements including Mg, P, S and the ionic salts Na, Cl and K.     

Substrate selection for optimum qualitative and quantitative single atmospheric particles analysis using nano-manipulation,sequential thin-window electron probe X-ray microanalysis and micro-Raman spectrometry

Sequential electron probe X-ray microanalysis using thin-window energy dispersive X-ray detection (TW-EDX-EPMA) and micro-Raman spectrometry (MRS) on the same atmospheric particle using nano-manipulation, is demonstrated. The advantageous combination of these two techniques allows information on the morphology, size, elemental and molecular composition, as well as the molecular structure of the same individual particle with a diameter as small as 500 nm. The use of an ultra-thin atmospheric window and a cold stage in EPMA enables qualitative and quantitative analysis of low-Z elements like C, N, and O as well as higher-Z elements. The work illustrates substrate optimisation and subsequent application in the analysis of atmospheric particles. Particle relocation was achieved by manipulative transfer onto transmission electron microscope grids, in an environmental scanning electron microscope, using 100 nm glass tips. A moderate correlation between the elemental composition obtained by TW-EDX-EPMA and the molecular fingerprint obtained by MRS is illustrated and its useful application in the interpretation of indoor air quality is discussed.     

Investigation of winter atmospheric aerosol particles in downtown Katowice using XPS and SEM.

X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemical composition of atmospheric particles (PM-10 and PM-2.5), collected in downtown Katowice, Upper Silesia, Poland, in the winter season (November and December 2000). Carbon- and oxygen-containing species dominated the particulate surface with traces of N, S, Si, Cl, Na, Zn, Al, Cu, Fe, Ca, K, Mg, Pb, and P present. Additionally, the size, morphology, and chemical composition of about 300 of the individual atmospheric particles were analyzed by high-resolution scanning electron microscopy and electron probe microanalysis. A number of aluminosilicates and metallic elements such as Fe, K, Mg, Zn, as well as rare earth elements, were detected by SEM. The results obtained show that the analyzed aerosol is of natural and anthropogenic origin. Particles containing sulfur compounds as well as oxygen and sodium in downtown Katowice come mainly from the east and southeast sectors.     

Elucidating a particulate matter deposition episode by combining scanning electron microscopy and X-ray fluorescence spectrometry.

Multielemental composition and morphology of particulate matter samples were examined to detect the presence of two potential responsible pollutant emitters at four sites impacted during a pollution episode in the City of Campana, Argentina. Coke and smoke black are the main constituents associated to the industrial plants that were considered, a priori, as responsible pollutant emitters. Wavelength dispersive X-ray fluorescence (WDXRF) was employed for the analysis of metals in samples coming from both, suspected sources and four sites. On the basis of multielemental composition profiles, a screening analysis was undertaken for exploring similarities among sources and sample sites adopting the average concentration profile of the crustal rock as soil surrogate. Particle morphology was studied by scanning electron microscopy (SEM) in source samples and in those environmental samples selected through the screening analysis. Two types of collected samples were analyzed: 1) those with composition profiles closer to the potential sources and 2) those closer to the cluster rock. This strategy was adequate to identify the responsible source of the contamination episode.     

Interfaced SEM/EDX and micro-Raman Spectrometry for characterisation of heterogeneous environmental particles — Fundamental and practical challenges

The molecular character of atmospheric particulate matter is of prime importance when interpreting air pollution trends and its subsequent influence on environmental monitoring and preventative conservation. The known methods of estimating the molecular composition normally involve elemental analysis of particles (both as bulk and computer controlled analyses of single particles) with subsequent multivariate analyses to clusterise the elements in groups of elements that are closely related to each other. With this approach one can at best suggest associations. Evidently the application of molecular spectroscopy in addition to elemental concentration profiles would provide intimate information regarding the nature of the particles and consequently their fate. This paper gives an overview of research performed in our laboratory and describes the optimisation of experimental parameters to use scanning electron microscopy with energy-dispersive X-ray detection (SEM/EDX) or electron probe X-ray microanalysis (EPXMA) in parallel with micro-Raman Spectrometry (MRS) to investigate single environmental particles. The challenges associated with the two stand-alone techniques are revealed and consequently those posed with an interfaced approach are discussed. Preliminary results, of an initial investigation of the SEM/EDX interfaced with MRS to ultra-fine heterogeneous environmental particles, are given.     

Copper(I) stabilized on N,N′-methylene bis-acrylamide crosslinked polyvinylpyrrolidone: An efficient reusable catalyst for click synthesis of 1,2,3-triazoles in water

N,N′-methylene bis-acrylamide crosslinked N-vinyl-2-pyrrolidone (NVPMBA) polymer was prepared via suspension polymerization technique and used as a polymeric support for the reduction of Cu(II) to Cu(I). It was observed that NVPMBA matrix facilitated the stabilization of Cu(I) particles. Furthermore, the copper supported polymer catalyst (CuNVPMBA) was characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis, transmission electron microscope (TEM), X-ray photoelectron spectra (XPS), inductively coupled plasma optical emission spectroscopy, and derivative thermogravimetry analysis. SEM showed that both the polymer and CuNVPMBA exhibit a spherical morphology. TEM revealed that copper nanoparticles formed on the polymer surface have an average particle size of 5.14 nm. XPS analysis confirmed the presence of Cu(I) and Cu(II) in the ratio 1:2. The copper content in CuNVPMBA was found to be 1.25 wt%. CuNVPMBA was found to be very effective in promoting the click reaction between terminal alkynes and azides in aqueous media in the absence of ascorbate or external base under mild conditions to form 1,2,3-triazoles in excellent yield with a copper loading as low as 0.2 mol%. The catalyst could be reused and recycled several times without significant loss of catalytic activity.     

Investigation of surface topography, morphology and structure of amorphous carbon films by AFM and TEM

Morphology and structure of amorphous carbon films deposited with a pulsed arc source (LASER-ARC) have been studied using microscopical methods (SEM, TEM and AFM), electron diffraction and spectroscopical investigation (EELS). The parameters of the arc source and the deposition conditions (substrate temperature) influence morphology and structure of deposited amorphous carbon films. Especially the incorporation and growth of particles, embedded in the film have been investigated. By particle analysis using an optical microscope a majority of particles that is smaller than 500 nm has been determined. The morphology has been also demonstrated similar by AFM and TEM images. Their number and size of particles is strongly influenced by the deposition temperature. The structure of amorphous film is characterized by the EELS-spectra, but the particle structure was not detectable.     

Characteristics of the aerosol particulates in the atmosphere in an urban environment at Faisalabad, Pakistan

Summary The deposition of trace and major elements from the atmosphere to the ground is an important factor for plants, animals and humans as well. Total suspended particulate matter was measured by a standard gravimetric technique. A scanning electron microscope was used for the evaluation of the size distribution and morphological structures of the aerosol particulates trapped on the surface of filter paper. The aerosol particulates were studied by a scanning electron microscope at various magnification. The trace elemental composition in the atmosphere of Faisalabad was studied by using instrumental neutron activation analysis (INAA) and atomic absorption spectrometry (AAS). Concentrations of 23 trace elements and a major one were determined in samples of aerosol particulates collected during a longe sampling period in the atmosphere at Faisalabad, Pakistan. Their amount was two times higher than the limits adopted by the U.S. Environmental Protection Agency for the urban environment.     

Atomic emission spectrometric analysis of airborne particulate matter by direct nebulization of suspensions into the inductively-coupled plasma

A method is described for the rapid, direct emission spectrometric determination of iron in airborne particulate matter collected on polystyrene fiber filters using a conventional high-volume sampler and a Japanese low-volume sampler. The suspension prepared by dissolving the filter material in xylene was directly nebulized into the inductivelycoupled plasma excitation source. An ultrasonic immersion device was used for stirring purposes. Particles within the size range 0.1–100 μm in diameter are collected on the high-volume filters, while the largest particles on low-volume filters do not exceed 10 μm in diameter. The difference in the particle size composition entailed the use of a separate set of standard suspensions for each sample type. Standard suspensions for calibration were prepared from NBS SRM-1648 (urban particulates) as originally received and from its ground powder for high-volume and low-volume samples, respectively. The relative standard deviation was usually below 5%, which is acceptable for large-scale air pollution survey work. The possibility of determining other major and minor elements in airborne particulate matter was also examined.     

Molecular and elemental characterisation of mineral particles by means of parallel micro-Raman spectrometry and Scanning Electron Microscopy/Energy Dispersive X-ray Analysis

The “fingerprinting” of a molecular structure obtained by micro-Raman spectroscopy (MRS) can be successfully complemented by means of X-ray spot analysis through the application of scanning electron microscopy equipped with an X-ray detector (SEM/EDX). The elemental composition revealed by SEM/EDX is essential for a correct interpretation of the collected Raman spectra. The results presented here illustrate how the two techniques can be combined to characterize geological samples, especially in the case of individual particles. The samples involved in the experiments were Zr- and Ti-bearing sand from South Africa (with major minerals such as zircon and rutile) and U mine tailings from Hungary (rich with feldspars, quartz and sulphate minerals). Mineral phases detected by MRS were identified according to their respective main Raman shifts, with a spatial resolution up to 1 μm, depending on the parameters set. Some unusual and sometimes inexplicable Raman activity was observed, which was ascribed to and rationalized by the presence of accompanying elements as detected with EDX. The relocation of a particle by means of the two instruments was facilitated with TEM grids. Although the limitations of the sequential use of SEM/EDX and MRS, such as different beam sizes, probing depth and surface topography, should be considered in their application to the analysis of individual geological particles, the two methods appeared to be complementary. Not only do they provide correlated chemical information about the sample, but also enable chemical characterization that would be otherwise incomplete when analyzed on a stand-alone basis.     

The continental component of a Pacific Marine aerosol: Identification by combined neutron activation analysis and scanning electron microscopy with X-ray analysis

The relative merits and sampling requirements of instrumental neutron activation analysis (INAA) and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis as applied to the continental component of marine aerosols are discussed. When correlated with air mass information, the quantitative INAA data on the concentrations of 15 major and minor elements in the continental dust fraction provides information on the geochemical type and location of the land source. Although the SEM/EDS technique provides only qualitative concentrations for 6 additional elements in the aerosol, the important feature of single particle analysis enables more nearly synoptic interpretation of aerosol composition and concentration. A combined INAA and SEM/EDS study of the aerosol samples is therefore preferred.     

Single-particle characterization of “Asian Dust” certified reference materials using low-Z particle electron probe X-ray microanalysis

In order to clearly elucidate whether Asian Dust particles experience chemical modification during long-range transport, it is necessary to characterize soil particles where Asian Dust particles originate. If chemical compositions of source soil particles are well characterized, then chemical compositions of Asian Dust particles collected outside source regions can be compared with those of source soil particles in order to find out the occurrence of chemical modification. Asian Dust particles are chemically and morphologically heterogeneous, and thus the average composition and the average aerodynamic diameter (obtainable by bulk analysis) are not much relevant if the chemical modifications of the particles must be followed. The major elemental composition and abundance of the particle types that are potential subjects of chemical modification can only be obtained using single-particle analysis. A single particle analytical technique, named low-Z particle electron probe X-ray microanalysis (low-Z particle EPMA), was applied to characterize two certified reference materials (CRMs) for Asian Dust particles, which were collected from a loess plateau area and a desert of China. The CRMs were defined by bulk analyses to provide certified concentrations for 13 chemical elements. Using the low-Z particle EPMA technique, the concentrations of major chemical species such as aluminosilicates, SiO₂, CaCO₃, and carbonaceous species were obtained. Elemental concentrations obtained by the low-Z particle EPMA are close to the certified values, with considering that the single particle and bulk analyses employ very different approaches. There are still some discrepancies between those concentration values, resulting from analyses of particles with different sizes, different sample amounts analyzed, and uncertainties involved in the single particle analysis.     

单分散性银纳米粒子的可控制备

以卤化银或氧化银作为前驱体,室温下以水为溶剂,在较高溶液浓度下,利用化学还原法制备了单分散性银纳米粒子,并通过改变前驱体的种类,实现了粒径可控制备。采取扫描电子显微镜（SEM）、紫外-可见光谱仪（UV-Vis）、X射线-粉末衍射仪（XRD）、X射线-光电子能谱仪（XPS）等对所制备的银纳米粒子的形貌及成分进行了表征。结果显示,所制备的银纳米粒子具有较高的单分散性,粒径在40~150 nm之间,具有面心立方多晶结构。该方法制备的银纳米粒子可用于喷墨打印RFID天线。     

The influence of collecting substrates on the single-particle characterization of real atmospheric aerosols

This work investigated the influence of three different collecting substrate materials, Ag and Al foils and grids for transmission electron microscopy (TEM grid), on the morphological and chemical compositional analysis of individual particles collected at an underground shopping area in Seoul, Korea. The feasibility of using each substrate in a quantitative single-particle analysis was evaluated by comparing particle morphologies, X-ray spectra, and elemental quantification results obtained for the three substrates. The morphologies and the quality of X-ray spectra for crystalline mineral particles were very similar among the three substrates. However, water-soluble, CNO-rich aerosols showed different morphologies among the three substrates, mainly due to the differences in the hygroscopic properties of the substrates. The quality of the X-ray spectra of the CNO-rich particles was optimal when collected on the TEM grid. To reliably assess the characteristic X-rays of the CNO-rich particles collected on the Ag and Al foils, appropriate data analysis had to be applied. Especially, the X-ray spectra of the CNO-rich particles collected on Al foil required a new background subtraction procedure. The overall relative abundances of the chemical species, obtained from the three collecting substrates, were in good agreement with each other and single-particle characterization of the real aerosol sample was feasible on the different substrates. However, the TEM grid substrate was the most appropriate for single-particle analysis of the water-soluble CNO-rich particles as: (i) it retains the original morphology and size of the particles, (ii) it allows high contrast in the backscattered electron image (BSEI) mode, and (iii) it provides a high peak-to-background ratio (P/B) with small and correctable interferences in the X-ray spectra.     

MORPHOLOGY EVOLUTION OF POLY（St-co-BuA）/SILICA NANOCOMPOSITE PARTICLES SYNTHESIZED BY EMULSION POLYMERIZATION

Poly（St-co-BuA）/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-（trimethoxysilyl）propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope （TEM） and scanning electron microscope （SEM） in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.     

Green synthesis and characterization of cobalt oxide nanoparticles and its electrocatalytic behavior

Green synthesis of pure cobalt oxide nanoparticles (CoO-NPs) in aqueous medium has been carried out using gelatin. The main advantage of using gelatin as a stabilizing agent is that it provides long-term stability for nanoparticles by preventing particles agglomeration. The particles have been characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), energy dispersive X-ray (EADX), and thermogravimetric analysis (TGA). TEM image shows the formation of CoO-NPs with average particle size of 28 nm which agrees well with the XRD data. Cobalt oxide nanoparticles modified carbon paste electrode (CoO-NPs/CPE) displayed excellent electrochemical catalytic activities towards the oxidation of glucose. The electrocatalytic response showed a wide linear range of 7–1000 µM, as well as its experimental limit of detection can be achieved 5.3 µM. The modified electrode for glucose determination is of the property of simple preparation, good stability and high sensitivity.     

十六烷基膦酸表面修饰纳米镍粉及其复合材料的制备和性能

以十六烷基膦酸作为修饰剂, 对纳米镍粉进行表面改性处理, 通过溶液共混的方法制备改性镍粉与聚丙烯的聚合物基复合材料. 利用X射线光电子能谱(XPS)、 X射线衍射(XRD)及透射电子显微镜(TEM)等测试手段研究改性镍粉的表面形态; 利用扫描电子显微镜(SEM)研究复合材料断面形貌; 利用介电频谱分析系统对复合材料的介电常数和介电损耗等进行了测试. 结果表明, 纳米镍粉表面形成厚度为2~4 nm的十六烷基膦酸包覆层, 使纳米镍粉由亲水性变为亲油性; 聚丙烯基复合材料中, 改性镍粉均匀分散; 复合材料的介电常数在镍填充量为40%时, 可以达到纯聚丙烯的近10倍.     

Investigation of individual micrometer-size Kosa particle with on-site combination of electron microscope and synchrotron X-ray microscope.

The Kosa (yellow sand) aerosol affects the global environment as well as human health because it migrates from the interior of China to other areas, absorbing various atmospheric elements. Investigation into individual Kosa aerosol particles, which are submicroscopic to several tens of micrometers in diameter, is required to resolving the issue. We installed a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDX) on a synchrotron radiation (SR) beam line and introduced the SR beam into the SEM chamber for combinatorial application of SEM-EDX and SR X-ray fluorescence (SR-XRF) spectrometry to individual particles. It should be noted that detailed topographic observation by SEM and sensitive elemental analysis by SR-XRF, both crucial for individual particle measurement but which previously had to be carried out separately, were jointly performed inside the SEM chamber in this setup. Here, we show that SR-XRF results, in conjunction with SEM images, contributed toward resolving individual particle dispositions. Atmospheric sulfur primarily adheres to calcium in the aerosol particles and the particle surface roughens as a consequence of the chemical reaction between the two elements.     

泡沫状二维复合材料的合成及超级电容器性能

利用蔗糖和乙醇作为碳源,以氯化镍高温还原形成的镍颗粒作为模板,制备了泡沫状石墨烯多孔材料。 继而以其作为载体,通过浸渍和高温热解法制备了泡沫状MoS₂/石墨烯二维复合材料。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉曼光谱、X射线衍射(XRD)等技术手段研究了复合材料的形貌、组成和结构。 循环伏安、恒流充放电和循环寿命测试均表明,该材料具有良好的超级电容器性能,质量比电容达203.5 F/g,面积比电容达280 mF/cm²,5000次恒流充放电循环后的电容保持率约80%。