Characterization and source identification of fine particulate matter in the atmosphere of downtown Shanghai using μ-SXRF and ICP-MS

To investigate the characteristic and sources of the free particulate matter (PM2.5), and the major sources affecting particulate air pollution in Shanghai, China, the individual aerosol particles were analyzed using the synchrotron radiation micro-beam X-ray fluorescence analysis (μ-SXRF), and the PM2.5 multi-elements were determined by the inductively coupled plasma mass spectrometer (ICP-MS). The results show that the mass concentration and chemical elements have seasonal variation, and the enrichment factors show that the chemical elements in the inhalable particles could come from the earth crust and anthropogenic pollution. The extent of metal pollution was assessed by comparing the measured concentrations with those reported in the literature. Nine categories of PM2.5 pollution sources identified at the center of Shanghai show that the vehicle exhaust, emission of metallurgic industry and coal combustion are important.     

Study of emission episodes of urban aerosols by ion beam analytical techniques

The quantitative elemental composition and morphology of over 500 atmospheric aerosol particles were determined by nuclear microscopy and scanning electron microscopy (SEM). The samples originated from eight sampling campaigns, when hourly variation and sources of the urban aerosol elemental components were studied in Debrecen between 2007 and 2010. Aerosol which could be connected to heavy metal pollution episodes and high aerosol pollution levels deposits were selected for the nuclear microprobe study.Ion beam analytical methods (micro-PIXE and STIM) provided the elemental composition of coarse (particles with aerodynamic diameter between 2.5 and 10 μm) aerosols while the morphology of the different particle types was determined by SEM.Through the elemental composition, elemental correlations and morphology different particle types were identified and attributed to different anthropogenic sources like biomass burning, oil combustion, traffic or industry.     

Aerosol composition and source apportionment in Santiago de Chile

Santiago de Chile, São Paulo and Mexico City are Latin American urban areas that suffer from heavy air pollution. In order to study air pollution in Santiago area, an aerosol source apportionment study was designed to measure ambient aerosol composition and size distribution for two downtown sampling sites in Santiago. The aerosol monitoring stations were operated in Gotuzo and Las Condes during July and August 1996. The study employed stacked filter units (SFU) for aerosol sampling, collecting fine mode aerosol (dp<2 μm) and coarse mode aerosol (210 mass of particles smaller than 10 μm) and black carbon concentration were also measured. Particle-Induced X-ray Emission (PIXE) was used to measure the concentration of 22 trace elements at levels below 0.5 ng m⁻³. Quantitative aerosol source apportionment was performed using Absolute Principal Factor Analysis (APFA). Very high aerosol concentrations were observed (up to 400 μg/m³ PM₁₀). The main aerosol particle sources in Santiago are resuspended soil dust and traffic emissions. Coarse particles account for 63% of PM₁₀ aerosol in Gotuzo and 53% in Las Condes. A major part of this component is resuspended soil dust. In the fine fraction, resuspended soil dust accounts for 15% of fine mass, and the aerosols associated with transportation activities account for a high 64% of the fine particle mass. Sulfate particle is an important component of the aerosol in Santiago, mainly originating from gas-to-particle conversion from SO₂. In the Gotuzo site, sulfates are the highest aerosol component, accounting for 64.5% of fine mass. Direct traffic emissions are generally mixed with resuspended soil dust. It is difficult to separate the two components, because the soil dust in downtown Santiago is contaminated with Pb, Br, Cl, and other heavy metals that are also tracers for traffic emissions. Residual oil combustion is observed, with the presence of V, S and Ni. An aerosol components from industrial emissions is also present, with the presence of several heavy metals such as Zn, Cu and others. A factor with molybdenum, arsenic, copper and sulfur was observed frequently, and it results from emissions of copper smelters.     

Size-resolved source apportionment of aerosol particles using polycapillary X-ray lens with a plateau in its focal spot

A laboratory micro X-ray fluorescence spectrometer based on a special polycapillary X-ray lens (PXRL) was used to carry out the source apportionment of aerosol particles. In the curve of the distribution of the X-ray intensity in the focal spot of the special PXRL, there was a plateau with a diameter of 21.3 μm in which the distribution of the X-ray intensity was homogeneous. The gain in flux density in the plateau of the PXRL is 1490. The uniformity of this plateau was 2.9%. This was helpful for the quantitative X-ray fluorescence analysis of a single aerosol particle with smaller size than that of the plateau of the PXRL. The fingerprint database of aerosol particles with given sizes from various air pollution sources was established with the single particle analysis method. The size-resolved source apportionment of aerosol particles in haze in Beijing city was performed with this fingerprint database.     

旋风组钠气溶胶去除系统性能验证

钠气溶胶是钠冷快堆发生钠火时产生的特征性产物,需通过除尘净化系统对钠气溶胶进行去除净化,以减少排放到环境的放射性剂量和钠气溶胶浓度。采用干式气固分离路线,设计了一套旋风组钠气溶胶去除系统,通过开展真实钠火环境下的钠气溶胶去除试验,考察了金属钠燃烧过程中钠气溶胶浓度变化、粒径分布、压降、去除效率等主要参数,最终认为该系统对钠气溶胶具有很高的去除效率。     

PIXE和XRF用于北京新镇地区PM2.5源解析研究

大气颗粒物(APM)对人体健康和环境的影响越来越受重视,我国增设了PM2.5标准,同时提出了大气污染的专项治理措施。本文采用GENT二级取样器在北京郊区新镇进行连续取样,并用质子激发X射线荧光分析和能量色散X射线荧光分析对北京新镇地区收集到的140个大气颗粒物样品进行了多元素分析,对测量数据进行了可靠性评价和数据重组,结合取样、气象等参数建立了新镇地区大气颗粒物污染成分数据库,利用正矩阵因子模型进行污染源解析研究。初步认定了5个主要污染源,即燃煤源(29.2%)、汽车尾气和垃圾焚烧源(26.2%)、建筑工业源(23.3%)、土壤源(15.4%)以及含氯工业源(5.9%)。并结合气象数据进行了污染源来源研究,根据条件概率函数和潜在源贡献函数的计算结果作出了污染源来源分布图,发现污染来源与周围环境基本符合。     

负载型多分散气溶胶在管道内的传输规律

放射性气溶胶的传输一直是倍受关注的环境问题。为研究放射性气溶胶在管道内的传输规律,首先自制了能够产生稳定的、多分散气溶胶的发生器。主要考察了稀释气流速（5~25 L/min）、气溶胶颗粒粒径（多分散体系）及固体颗粒密度（土壤、石英砂）对气溶胶在管道内传输的影响。即考察了粒径多分散的石英砂、土壤颗粒形成的气溶胶及表面负载Ag的石英砂颗粒模拟负载型放射性气溶胶,在不同稀释气流速作用下进入管道内的传输,针对每一节管道内的沉积物进行收集分析,从而得到气溶胶在管道内的传输及沉降规律。研究结果表明：密闭管道内,在一定流速范围内,沉积物最高频度粒径随着管道距离的增长而先增大后减小;小粒径的颗粒在传输过程中自重沉降,且由于布朗运动吸附在大粒径颗粒物表面加速其沉降速率,即减小了其在管道内的传输距离;表面负载Ag的石英砂颗粒形成的气溶胶随着稀释气吹扫导致Ag和石英砂颗粒之间有不同程度的分凝,气流速率越大,分凝现象越明显。     

核分析技术在环境和医学研究中的应用

通过对汽车尾气颗粒物、同一污染源的不同粒径飞灰样品的分析,以及稀土元素对人和动物的毒性研究,获得了环境监测和方面的特定信息,展现了核分析技术在环境和医学中的广泛应用。     

Roadside dust contamination with toxic metals along industrial area in Islamabad,Pakistan

An investigation has been carried out to understand the contamination characteristics of roadside dust in the industrial area of Islamabad, Pakistan. The amounts of Si, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Zn, Ga, As, Se and Cd were determined from 95 roadside dust samples collected along the Islamabad industrial area using Proton Induced X-ray Emission （PIXE）. The results indicated that concentrations of all elements, except Cd, in the roadside dust were significant. The results of the enrichment factor show that the elementary composition of the roadside dust could be categorized as soil elements from the crust of the earth and elements from anthropogenic pollution. The high enrichment factors imply that elements such Cr, Cu, Pb, Zn, As, Se, Cd, Ni, Co and S came from anthropogenic activities. The source of metal contamination was identified using multivariate statistical analysis. It has been concluded that Ca, Sc, Ti, V, Mn and Fe mainly originate from crustal sources; Cr, Cu, Ni, Pb, Zn and Ga are associated with point-sources from industrial pollution/traffic; and S, Cl, K, As and Se are mainly related to oil/coal combustion.     

Identification and characterization of fine and coarse particulate matter sources in a middle-European urban environment

In this work a source apportionment study is presented which aimed to characterize the PM_2.5 and PM_2.5–10 sources in the urban area of Debrecen, East-Hungary by using streaker samples, IBA methods and positive matrix factorization (PMF) analysis.Samples of fine (PM_2.5) and coarse (PM_2.5–10) urban particulate matter were collected with 2 h time resolution in the frame of five sampling campaigns during 2007–2009 in different seasons in the downtown of Debrecen.Elemental concentrations from Al to Pb of over 1000 samples were obtained by particle induced X-ray emission (PIXE); concentrations of black carbon (BC) were determined with a smoke stain reflectometer. On this data base source apportionment was carried out by using the PMF method.Seven factors were identified for both size fractions, including soil dust, traffic, secondary aerosol – sulphates, domestic heating, oil combustion, agriculture and an unknown factor enriched with chlorine. Seasonal and daily variation of the different factors was studied as well as their dependence on meteorological parameters.Besides determining the time patterns characteristic to the city, several emission episodes were identified including a Saharan dust intrusion on 21st–24th May, 2008.     

Analysis of atmospheric aerosols by PIXE: the importance of real time and complementary measurements

Particle-Induced X-ray Emission (PIXE) has been used for more than 30 yr in many urban and background air pollution studies. The technique has certainly contributed to the understanding of source-receptor relationship for aerosol particles as well as to aerosol physics and chemistry. In the last few years, where aerosol issues were strongly linked to global climate change through the relationship between aerosol and atmospheric radiation points to new challenges in atmospheric sciences, where PIXE could play an important role. Also the recognition for the inter-relationship between aerosol and liquid and gas phases in the atmosphere makes important to integrate PIXE aerosol analysis with other complementary measurements. The use of Nephelometers and Aethalometers to measure scattering and absorption of radiation by aerosol particles can be done in parallel with particle filter collection for PIXE analysis. Parallel measurements of trace gases using traditional monitors as well as with new techniques such as Differential Optical Absorption Spectroscopy (DOAS) that can provide concentration of O₃, SO₂, NO₃, NO₂, HCHO, HNO₃, Benzene, Toluene, and Xylene, is also important for both urban and remote aerosol studies. They provide information that allows a much richer interpretation of PIXE data. Recently developed instruments that provide real time aerosol data such as the Tapered Element Oscillating Microbalance (TEOM) PM₁₀ monitor and automatic real time organic and elemental carbon analyzers provide extremely useful data to complement PIXE aerosol analysis. The concentrations of trace elements measured by PIXE comprise only 10–30% of the aerosol mass, leaving the organic aerosol characterization and measurement with an important role. The aerosol source apportionment provided by PIXE analysis can be extended with other aerosol measurements such as scattering and absorption, estimating for example, the radiative impact of each discriminated aerosol source. The aerosol bulk PIXE measurements can be complemented with soluble concentrations provided by Ion Chromatography (IC) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Recent developments in remote sensing techniques and products also enhance significantly regional aerosol studies. Three-dimensional air mass trajectories should be integrated in aerosol studies for urban and remote areas. The applications of these techniques to study urban aerosols from São Paulo and Santiago de Chile have broadened extensively the scientific scope of these studies.     

SPM analysis on groups of single aerosol particles around steel plant

Several methods for preparing samples of dispersed single aeroslo particles used in scanning proton microprobe(SPM) analysis were tested.Many elements such as Al,Si,S,Cl,Ca,Ti,Cr,Mn,Fe,Ni,Cu and Zn in the groups of different single aerosol particles from the Capital Steel Plant area were analyzed by SPM,The distributions of elemental contents in the group of single particles were mapped with three dimensional contour and the isometric.A new approach to study the group of different single aerosol particles for air pollution is developed in the present work.The results are significant to assessing the environmental impact of the dispersed single aerosol particles.     

Source–receptor relationships for heavy metals in the European atmosphere

Atmospheric concentrations of heavy metals (HMs), in particular As, Cd, Cu, Pb and Zn, were studied in an effort to contribute to the understanding of European source-receptor relationships. A comparison was made between the ambient concentrations measured at 11 background aerosol monitoring stations (in Denmark, the Czech Republic, Finland, Norway and Sweden) and the corresponding HM concentrations estimated by the Heavy Metals Eulerian Transport (HMET) meteorological dispersion model. The collected samples were analysed with Particle Induced X-ray Emission analysis (PIXE) except the Finnish samples which were analysed with Inductively Coupled Plasma – Mass Spectrometry (ICP-MS). The available data covers the period 1985–1994. The comparison showed that the European emissions of As, Cd and Pb seem to be fairly well estimated. On the other hand, the European Zn emissions are underestimated by a factor of 3 or more, while the Cu emissions appear to be slightly overestimated. The HMET dispersion model also made it possible to select occasions for which the sampling sites had a substantial contribution of HM from the highly polluted “Black Triangle” region (on the borders between the Czech Republic, Poland and Germany). The time evolution of the sources of HMs within this source region could be studied by applying various statistical receptor models on the extensive data set from two Danish stations, Keldsnor and Tange, covering the period 1985–1994. Four source types were clearly discerned throughout the 10 year time period. These sources were: soil dust; sea spray; general combustion and oil combustion. The strong time-dependence observed for the contribution from the Black Triangle region emphasizes the importance of keeping the emission inventories continuously updated if HMs deposition calculations and HMs emissions reduction protocols are to be based on dispersion modelling approaches.     

基于扫描核探针技术的大气气溶胶单颗粒物源识别与解析方法研究与应用

将高分辨、高灵敏的扫描核探针(SNM)技术与人工神经网络(ANN)模式识别方法相结合,以单个气溶胶颗粒物化学表征为基础,开展大气气溶胶源识别与解析的新方法研究。摸索出单颗粒气溶胶SNM靶样的制备方法。建立了SNM多站多参量分析模式的数据获取系统和分析条件。用SNM测定了单个大气气溶胶粒子的元素谱特征。基于标准的误差反向传输神经网络算法,建立ANN模式识别系统,直接对单个气溶胶粒子的SNM分析能谱模式进行识别,判别其来源,计算源的贡献率。将建立的方法初步应用于上海市大气PM10源识别与解析研究。结果表明该方法解析能力强,解析结果客观,具有查找未知污染源、解析低浓度污染源的特点。     

Analysis of atmospheric aerosols by particle-induced X-ray emission, instrumental neutron activation analysis, and ion chromatography

Particle-induced X-ray emission (PIXE), ion chromatography (IC), and occasionally also instrumental neutron activation analysis (INAA) were used in combination for the analysis of atmospheric aerosol samples that were collected on Nuclepore polycarbonate filters. A comparison of the results enabled us to evaluate the matrix effects (i.e., particle size effects) of the PIXE analysis for the light elements and to assess the water-solubility and/or speciation of a number of elements (e.g., S, K, Ca). Results are presented from several measurement campaigns at urban and forested sites in Europe, whereby PM10 or PM2.5 filter samples were taken. From the PIXE and IC results for a 2003 summer campaign at the K-puszta site in Hungary, it was estimated that organosulphates could be responsible for 20% of the total sulphur concentration and 30% of the organic aerosol in PM10. The comparison of the IC and PIXE data for K and Ca from the various sites indicated that most of the Ca was water-soluble (the mineral dust Ca was presumably mostly present as calcite, and perhaps also in part as gypsum); in contrast, for K, only half of it was typically water-soluble, indicating that it was to a large extent associated with insoluble mineral dust. Exceptions, with almost fully water-soluble K, were found for samples that were substantially impacted by biomass burning.     

Ion beam microanalysis of individual aerosol particles originating from Saharan dust episodes observed in Debrecen,Hungary

Approximately 50 episodes of Saharan dust intrusion have been observed by PIXE in the atmosphere of Debrecen, Hungary since 1991 [I. Borbély-Kiss, Á.Z. Kiss, E Koltay, Gy. Szabó, L. Bozó, J. Aerosol Sci. 35 (2004) 1205]. In order to separate dust particles of Saharan origin from local sources, and to follow the formation, ageing and evolution of particles originating from long range transport processes, individual dust particle analysis was carried out on the Debrecen ion microprobe.The samples were collected on polycarbonate filters at a rural site 50 km from Debrecen during the Saharan sand plume in November 1996.Quantitative elemental concentrations for elements Z ? 6 were determined using PIXE–PIXE and STIM analytical methods. Saharan dust particles were selected on the base of characteristic elemental ratios like Ti/Ca, Ti/Fe and Al/Ca. Major and trace element content and possible chemical composition of the selected particles were determined.Single particle analysis of Saharan dust particles will lead to a better understanding of their formation process during transport.     

Controlling fine particles in flue gas from lead-zinc smelting by plasma technology

With the aim of controlling the problem of fine particles in the flue gas of lead-zinc smelting, a low-temperature plasma-electrocoagulation and electric bag composite dedusting experimental platform was designed by combining electrocoagulation and electric bag composite dust removal technology based on the research of low-temperature plasma technology. Firstly, the properties of fine particles in flue gas from lead-zinc smelting were analyzed, and the effects of input voltage, filter wind speed, dust concentration, and pulse-jet ash-cleaning cycle on the dust collection efficiency of the integrated device were studied. Then, the energy efficiency of the integrated technology was analyzed, and the control mechanism of the fine particles was revealed. The experimental results show that the integrated technology of low-temperature plasma-electrocoagulation and electric bag composite dust removal achieves a fine particle removal efficiency of more than 99.99% and the energy consumption per unit mass of the dust is only 0.008 k W·h/g. The integrated technology has broad application prospects and farreaching practical significance for the lead-zinc smelting industry to achieve ultra-low emission targets for flue gas and achieve energy-saving and emission reduction effects.     

PIXE investigation of aerosol composition over the Zambian Copperbelt

Atmospheric sulphate aerosol concentrations are of interest in climate change studies because of their negative climate forcing potential. Quantification of their forcing strength requires the compilation of global sulphur emission inventories to determine the magnitude of regional sources. We report on measurements of the ambient aerosol concentrations in proximity to a copper refinery in the central African Copperbelt, along the border of Zambia and the Democratic Republic of the Congo. This region is historically regarded as one of the largest African sources of sulphate aerosols. Sulphate is produced by oxidation in the atmosphere of SO₂ emitted during the pyrometallurgical processing of Cu–Co sulphide ores. Since the last quantification of sulphur emissions (late 1960s), there has been large-scale reduction in copper production and more frequent use of the leaching technique with negligible sulphur emissions.

Samples were collected over four weeks, November–December 1996, at Kitwe, Zambia. A low volume two-stage time-resolving aerosol sampler (streaker) was used. Coarse and fine mode aerosols were separated at >2.5 and >10 μmad. Hourly elemental concentrations were determined by 3.2 MeV PIXE, and routinely yielded Si, S, K, Ca, Ti, Mn, Fe, Cu and Zn, above detection limits. Si, K, Ca and Fe (major crustal components) dominated the coarse elemental mass. In the fine stage, S and Si accounted for up to 80% of the measured mass, and S alone up to 60%. Time series analysis allowed the division of sulphur and crustal elements (Si, K, Ca, Fe) between (i) background concentrations representative of synoptic scale air masses; and (ii) contributions from local sources, i.e., copper smelter and re-suspended soil dust. Short duration episodes of S concentrations, up to 26 μg/m³, were found simultaneously with enhanced Cu, Fe and Zn. Contributions from individual pyrometallurgic processes and the cobalt slag dump could be distinguished from the elemental signatures. Periods of diminished sulphur concentrations were also identified, indicating a well-mixed regional air mass. These results will contribute towards validating global climate model predictions of aerosol forcing over central Africa.     

一种用于SPM分析的大气气溶胶单颗粒样品的制备方法

介绍了一种用于扫描质子微探针分析的大气气溶胶单颗粒样品的制备方法。通过实验摸索出一种适合于支撑颗粒物的材料聚乙烯醇缩丁醛(PVB)。大气颗粒物被直接采集在PVB薄膜上从而制成样品,保持了颗粒物的原始信息。用显微镜观察了采集的颗粒物,颗粒物之间完全分开,颗粒物间距合适。样品的扫描质子微探针试验结果表明,所制成的单颗粒样品能经受住质子束的长久轰击。对PVB薄膜的本底测试表明,这种膜的本底很小,不会对被测颗粒物的元素产生干扰。