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。     

Source apportionment of single aerosol particles in the atmosphere of Shanghai city

A nuclear microprobe with high spatial resolution and high analytical sensitivity was applied to analyze atmospheric aerosol at five monitoring sites in Shanghai city.Meantime,a new pattern recognition technique,which used the micro-PIXE spectrum of a single aerosol particle as its fingerprint.was developed to identify the origin of the particle.The results showed that the major contributors to the atmosphere pollution were soil dust(31.6%) ,building dust(30.8%),and the next were vehicle exhaust(13.7%),metallurgic industry excrements(5.6%).oil combustion(5%) and coal combustion(2.3%).Besides these ,about 10% of the particles could not be identified.Based on the cluster analysis of these particles.they could be divided into eight groups.By inference,they might belong to some sub-pollution sources from soil dust,building dust and metallurgic industry excrements.Moreover,some new pollution sources from tyres and chemical plants were also revealed.     

核分析相关技术用于上海市大气污染特征研究

本文研究了近年来上海市区和郊区大气气溶胶颗粒物的污染状况,采用的多种核分析方法及相关技术有质子激发X荧光分析(PIXE)、激光粒径谱仪(LPS)、同步辐射X射线吸收精细结构(XAFS)和扩展X射线吸收谱精细结构(EXAFS)分析等先进技术.充分发挥核分析技术高灵敏度、快速无损、多元素微量微区同时分析的优势,从大气颗粒物的形貌特征、粒径分布、质量浓度、元素浓度、化学价态等入手,对上海大气可吸入颗粒物PM23和PM1o展开多方位的综合研究.     

草酸铈和草酸铀的热分解机理及煅烧遗传性北大核心CSCD

在核燃料后处理过程钚尾端处理中,通常利用草酸制备草酸钚沉淀然后进一步煅烧获得氧化钚颗粒、用于MOX燃料的制造,因此掌握草酸钚热分解机制、控制氧化钚产品颗粒的形貌和粒度具有实际意义。针对草酸盐的热分解机理和沉淀在煅烧后颗粒形貌遗传性问题,本工作选用草酸铈和草酸铀作为研究对象,系统研究了草酸铈、草酸铀的热分解反应,结合同步热分析仪(TG/DSC)与X射线衍射仪(XRD)的表征,获得了草酸铈和草酸铀的热分解数据;制备了不同粒度的草酸铈和草酸铀,用激光粒度仪考察了煅烧前后颗粒的粒度,并用扫描电镜(SEM)观察颗粒聚集状态、粒度和形貌,结果表明煅烧分解会导致粒径有规律地下降,但形貌得以保留。     

Investigation of loss factors of aerosol particles in the sampling systems of a nuclear power plant

The loss factor of particles with different sizes in a sampling system of a nuclear power plant has been experimentally determined. As shown by optical particle size measurements, the particle size distribution of the test aerosol titanium dioxide (aerodynamic diameter between 0.6 and 8 μm) agrees well with that of the ambient aerosol in the nuclear power plant. The total loss factor for titanium dioxide lies between 1.3 and 1.6. This means a loss of particles of about 23–38% and shows that the transfer properties of the sampling system are good. The experimental results for small particles (aerodynamic diameter 0.6–8 μm) are in good agreement with those of theoretical estimations. The transfer properties of the sampling system for larger particles (aerodynamic diameters up to 3 mm) have been investigated, too. The results of the measured loss factors show that the sampling system is suitable even in this case.     

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.     

Characterization of individual aerosol particles from the eruption of Lonquimay volcano in Chile

A set of aerosol samples collected during major volcanic activities around the Chilean site Lonquimay in the years 1988–1990 has been subjected to measurements in conventional and microPIXE modes in the Debrecen institute. The aim of the study was the completion of the earlier results with comparative PIXE data and microPIXE measurements for the characterization of individual particles. Results have been obtained on separate particles in terms of their elemental composition, on separate particle groups of different composition by statistical dissimilarity analysis. Si/Al and K/Si elemental ratios have been used for a comparison with published data from other volcanic locations.     

冬季上海吴淞地区大气颗粒物PM10的元素主成分分析

从2002年12月到2003年2月,利用8通道采样器对上海吴淞地区进行3个月的大气气溶胶PM10(空气动力学直径小于10μm的颗粒)的采样。使用质子激发X射线荧光(PIXE)分析方法进行了多元素质量浓度测定,然后对获取数据进行主成分分析,讨论了吴淞地区8个风向采集的PM10中含有的主要化学元素成分和可能的来源。     

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.     

激光烧蚀铀材料生成铀微粒的形态学研究

本文以激光器作光源,利用激光的高温烧蚀特性,以激光束烧蚀金属铀和二氧化铀材料,模拟高温条件下形成铀微粒的过程,用扫描电子显微镜和透射电子显微镜对铀材料及产生的含铀微粒的形态学特点进行了表征。实验表明,在激光束的轰击下,两种靶材料均出现熔化现象,铀金属表面呈现明显波纹状结构,二氧化铀的表面轰击边缘处呈现趋球状物堆积。生成的铀氧化物微粒为μm级形态不规则微粒及1 μm左右的球形微粒,说明铀在高温过程中产生球形微粒。对比研究了来自高温爆炸过程的金属银微粒,进一步验证了高温高压过程会产生球形微粒。结果表明,密实的铀氧化物微球是铀材料参与高温化学过程的结果,与低温过程中的剥蚀作用有明显的差别,是高温化学过程的特征,这为高温高压环境中的微粒分析提供了参考依据。     

De-agglomeration mechanisms of TiO2 aerosol agglomerates in PWR steam generator tube rupture conditions

A steam generator tube rupture (SGTR) in a pressurized water reactor (PWR) might be a major source of accidental release of radioactive aerosols into the environment during severe accident due to its potential to by-pass the reactor containment. In the ARTIST program, tests were carried out at flow conditions typical to SGTR events to determine the retention of dry aerosol particles inside a steam generator tube. The experiments with TiO₂ agglomerates showed that for high velocities in the range of 100-350 m/s, the average particle size at the outlet of the tube was significantly smaller than at the inlet due to particle de-agglomeration. Earlier, particle de-agglomeration has not been considered significant in nuclear reactor severe accidents. However, the tests in ARTIST program have shown that there is a possibility that TiO₂ aerosol particles de-agglomerate inside a tube and in the expansion zone after the tube exit under SGTR conditions.In this investigation, we measured TiO₂ aerosol de-agglomeration in the tube with very high flow velocities with two different TiO₂ aerosols. The de-agglomeration was determined by measuring the size of the agglomerates at the inlet and outlet of the test section. The test section was composed of tubes with three different lengths, 0.20, 2.0 and 4.0 m, followed by an expansion zone.The main results were: (i) the de-agglomerate process was relatively insensitive to the initial particle size distribution, (ii) the agglomerates were observed to de-agglomerate in all the tubes, and the resulting particle size distributions were similar for both TiO₂ aerosols, (iii) at high flow rates, increasing the gas mass flow rate did not produce further de-agglomeration, and (iv) the agglomerates did not de-agglomerate to primary particles. Instead, after de-agglomeration the particles had a median outer diameter D_c = 1.1 μm. Based on analysis using computational fluid dynamics (CFDs), the de-agglomeration was caused by the turbulent shear stresses due to the fluid velocity difference across the agglomerates in the viscous subrange of turbulence.It has to be noted that the particles used in this investigation were TiO₂ agglomerates, and not prototypical nuclear aerosols with significantly different characteristics. Therefore, the results of this investigation cannot be directly used to determine whether the nuclear aerosol particles may de-agglomerate in SGTR sequences. However, this investigation highlights the possibility of particle de-agglomeration under SGTR conditions, and identifies the mechanism of the de-agglomeration inside the broken tube and when the aerosol is discharged to an open space.     

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.     

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.     

基于热电离质谱的单微粒铀同位素分析方法比较

在核保障中,测定擦拭样品单微粒中铀同位素比可为探测未申报或隐匿的核活动提供重要的信息。裂变径迹 热电离质谱（FT TIMS）是该领域中的主流技术之一,近年来提出了一种新技术——扫描电子显微镜 热电离质谱（SEM TIMS）。本文通过对标准微粒样品的测定系统评估比较了该两种方法。该两种方法的测量结果均与标准微粒的参考值吻合较好,FT TIMS易于寻找、定位易裂变核素,对高浓铀具有极高的灵敏度。SEM TIMS则更易于同步开展含铀微粒形貌学和元素组成等分析,可视作FT TIMS有益的补充。     

Two years of aerosol pollution monitoring in Singapore: a review

An aerosol sampling campaign was initiated more than two years ago in Singapore. The aim was to determine the average elemental concentrations in fine and coarse aerosol fractions as well as to identify major pollution sources and their impact. For that purpose, two air samplers were employed at two different sampling locations; one sampler was a fine particulate aerosol sampler (PM2.5) located at the vicinity of a major industrial area. The other was a stacked filter unit (SFU) sampler designed for collection of fine and coarse fractions (PM2.5 and PM10) and installed in the residential area. Samples were taken typically twice a week and in several occasions daily. During the period of two years more than 700 aerosol samples were collected and analyzed using PIXE and RBS techniques. All samples were analyzed for 18 elements ranging between Na, Mg, Al, etc. up to As and Pb. Large daily and seasonal variations were found for most of the elements. These variations are attributed mainly to meteorological changes, in particular changes in wind speed and direction. On several occasions, short term sampling was performed to identify fingerprints of major pollution sources such as road traffic, refineries, as well as the rain-forest fires in neighboring countries. A summary of our findings is presented and discussed.     

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.     

In situ characterization of micron-scale particles by nuclear microscopy

Nuclear microscopy is well suited for analyzing large particle populations as well as individual particles of interest in various types of collection samples. Unlike some commonly used in situ techniques, nuclear microscopy can quantitatively characterize particles embedded within the sample or particles that are too small to be reliably removed from their collection media. Additional advantages include its capability for the detection of minor and trace elements, its capability to simultaneously analyze multiple elements with little or no prior sample preparation, and its potential for automated analyses. Preliminary data are presented of particle size and composition measurements conducted on air filters. The potential of applying nuclear microscopy to the cataloging of micron-scale cometary remnants captured in low density aerogel collectors is also explored. Because of its importance to a variety of collection programs, an innovative high-throughput ion beam imaging and analysis system is being jointly developed by Sandia and Lawrence Livermore national laboratories for rapid quantitative particle characterization.     

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.     

Composition of urban and rural aerosol samples collected in the Great Hungarian Plain

Urban and rural atmospheric aerosol samples have been collected simultaneously during 1997 in the Great Hungarian Plain. The elemental composition of the coarse and fine mode aerosol have been determined by the Proton-Induced X-ray Emission method. From the observed elemental concentrations, seasonal variations and variations with the wind sector distributions were found for separate elements. Principal component analyses gave four factors in urban aerosol, and three factors in the rural one. The order of the factors in the coarse mode aerosol is different from the order, found in the fine mode.