一个PIXE-RBS离子束分析系统的刻度

四川大学原子核科学技术研究所依托2.5 MeV范德格拉夫静电加速器搭建了质子诱发X射线荧光分析(Proton Induced X-ray Emission,PIXE)与卢瑟福背散射分析(Rutherford Backscattering Spectrometry,RBS)相结合的离子束分析系统,描述了该分析系统和刻度过程。通过10个金属单质的PIXE-RBS测量,刻度得到的仪器常数H值是一条随能量变化的曲线,然后采用最小二乘法拟合确定了X射线探测器前的Mylar膜有效厚度、选择性滤膜的有效厚度和中心小孔大小,从而得到H值。为了对刻度H值进行检验,在相同实验条件下测量了标准粘土样品元素成分,测量数据与证书数据符合得较好。刻度结果将用于以后的PIXE-RBS分析。     

PIXE analysis of airborne particulate matter from Monterrey, Mexico. A first survey

A first survey of elemental contents in airborne particulate matter from Monterrey, Nuevo León, Mexico, was performed using PIXE. This second largest industrial city is located 715 km north of Mexico City, and counts with a population of nearly three million inhabitants in its conurbation. Air pollution in the place comes from a great variety of industries ranging from iron smelters to furniture manufacturing, as well as from fuel combustion in vehicles and industries. This study presents results of elemental contents in airborne particulate matter in two particle size fractions: PM_2.5 and PM₁₅. The samples were collected during five weeks on working days, Monday–Friday, from 9 December 1996 to 14 January 1997. Two samples a day were collected, 12 h each, night-time and day-time. These first results show local pollution as typical from a large urban area in conjunction with an active industry. Thirteen elements were consistently detected in most of the samples and some episodes due to both industrial and human activities were identified. A general discussion about the results obtained is presented.     

Effect of the amount of trapped particulate matter on diesel particulate filter regeneration performance using non-thermal plasma assisted by exhaust waste heat

An experimental system of diesel particulate filter(DPF) regeneration using non-thermal plasma(NTP) technology assisted by exhaust waste heat was conducted and regeneration experiments of DPFs with different amounts of trapped particulate matter(PM) were conducted. The concentrations of the PM decomposition products(COx) and the internal temperature of the DPF were monitored to determine the performance of DPF regeneration and thermal safety of the NTP technology. The results showed that the concentrations of CO and CO_2 and the mass of PM decomposition increased with the increase in the amount of captured PM, whereas the concentration of the NTP active substance(O_3) escaping from the DPF decreased under the same working conditions of the NTP injection system. A higher amount of captured PM promoted the oxidative decomposition reaction between NTP and PM and improved the utilization rate of the NTP active substances. The peak temperature at the same measuring point inside the DPF generally increased and the phases of the peak temperature were delayed as the amount of captured PM increased. The temperature peaks and temperature gradients during the DPF regeneration process were far lower than the failure limit value, which indicates that NTP regeneration technology has good thermal durability and increases the service life of the DPF.     

Chemical speciation of chlorine in particulate matter by wavelength-dispersive PIXE technique

Chemical speciation of chlorine (Cl) in atmospheric particulate matter (APM) was performed by using a wavelength-dispersive PIXE spectrograph based on high-resolution measurement of Cl-Kβ emission. Samples of atmospheric particles were size-fractioned and collected by a cascade impactor at an urban area in Tokyo. The target position with respect to the spectrograph was precisely adjusted by a 2D laser displacement sensor to achieve high detection efficiency. The samples were irradiated with 2 MeV protons from a tandem electrostatic accelerator. The beam current was 300-500 nA. During the irradiation, the target was cooled by liquid nitrogen to avoid the evaporation of volatile Cl compounds. The measured spectra for the NaCl standard samples clearly showed the Cl-Kβ series composed of the Kβ₁ and the satellite Kβ_x, Kβ₅ lines. From the measured X-ray yields, it was found that the chemical speciation of samples with Cl concentrations as low as ≈1% is possible by this method. The Cl-Kβ series were also successfully observed in the case of APM samples with particle sizes of 11.0-2.1 μm. The spectra shapes of the NaCl standard samples and an APM sample were slightly different from each other, because of some possible mixing of non-sea salt component in the APM sample.     

PIXE analysis of airborne particulate matter from Xalostoc, Mexico: winter to summer comparison

A study of elemental contents in airborne particulate matter from the industrial city of Xalostoc, Estado de México, was performed using PIXE. The place has a great variety of industries, it is a heavily populated, and it is a part of Mexico City's conurbation, thus contributing significantly to its atmospheric pollution. At present, there is few information available about elemental contents in airborne particulate matter from that region. In this study, two sets of samples of airborne particulate matter were collected daily during periods of four weeks in summer 1996 and winter 1997; two samples a day, 12 h each, night-time and day-time. Results revealed important information about elemental contents in airborne particulate matter from that area, especially in the respirable fraction PM_2.5. Comparison of night and day figures showed the presence of some elements such as Cu, Zn, and Pb, attributed, as it was expected, to uninterrupted industrial processes. Appearance of some other elements was more consistent only in either day-time or night-time due to diurnal or nocturnal industrial activities, or produced by human activities such as fuel combustion of automotive vehicles. Comparison of winter to summer results showed some other important features such as higher concentrations of pollutants in winter, because of the dry and cold weather, while summer samples exhibited lower concentrations mainly due to the presence of rain showers.     

用X射线吸收近边结构谱研究大气颗粒物中元素的种态

大气颗粒物中元素的种态研究,对评价其毒性和污染来源等有很重要的意义。本工作采集了不同地点和不同粒径的大气颗粒物样品,测定了样品中铬、锰、铜和锌的X射线吸收近边结构(XANES)谱,利用该谱分析了这些元素在颗粒物中的种态。结果显示,所采集的样品中铬主要以三价形式存在,锰主要以二价形式存在,铜也以二价形式存在,而锌主要以硫酸盐存在。用质子激发X射线荧光(PIXE)法测定了这些元素在样品中的浓度,观察到不同采样点和不同粒径的颗粒物中金属含量的差别,但未看到种态的这种变化。     

Manganese survey in airborne particulate matter from a mining area at Hidalgo State, Mexico

A manganese (Mn) survey in airborne particulate matter from a mining area located in Hidalgo State (Mexico) was performed using PIXE. Deposits of Mn ore, first discovered in 1959 and under continuous exploitation since 1962, are nowadays considered as one of the most important of their kind in the American Continent. Afterwards, local inhabitants have been under continuous overexposure to dusts and water highly enriched with Mn. Since no information was available about Mn content in airborne particulate matter in that area, especially in the respirable fraction PM_2.5, airborne particles were collected simultaneously at two sites located on opposite sides of the rim of the mining valley, and along the line of prevailing local winds. The sample collection was performed on eight alternate days, taking two samples per day (day-time and night-time) at each sampling site, using Stacked Filter Units (SFUs) of the Davis design to separate particles into fine (PM_2.5) and coarse (PM₁₅) sizes. The samples were PIXE analyzed and the results of this study revealed that Mn content, in both fine and coarse fractions, were in excess of the general urban background level of 40 ng/m³ (US Environmental Protection Agency, 1990) in more than 50% of the samples, which indicate severe environmental deterioration in the place under study.     

Study of particulate emissions near a steel plant in Genova by continuous sampling and PIXE hourly analysis

The particulate emissions near a large steel plant located in a densely inhabited suburb of the town of Genova (Italy) have been studied for a period of six months. We have used two-stage continuous streaker samplers and subsequent PIXE analysis with hourly resolution, to follow both seasonal and daily trends. The first streaker sampler remained installed very close to the plant cokery and furnaces, while another sampler was moved to different locations. Samples have been analysed by PIXE, deducing concentrations for elements from Na to Pb. During part of the campaign, the aerosol fractions with aerodynamic diameter (D_ae) < 2.5 μm (fine fraction) and with 2.5 < D_ae < 10 μm (coarse fraction) have been separately collected. We have measured and analysed about 8500 PIXE spectra: the steel plant emissions have been identified to some extent and resolved from other aerosol sources.     

Particulate matter in exhaled breath condensate: A promising indicator of environmental conditions

Assessing the retention of aerosol particles in the human lung, one of the most important pathways of absorption, is a demanding issue. At present, there is no direct biomarker of exposure for the respiratory system. The collection of exhaled breath condensate (EBC) constitutes a new non-invasive method for sampling from the lung. However, the heterogeneity of the sample due to particulate matter suspended in the condensed phase may influence the quality of analytical results in occupational assessments.The main objective of the study was to confirm the presence of particulate matter in the condensate, to investigate how large the particles in suspension could be and to determine their elemental contents relative to those of EBC matrix.This paper reports on preliminary nuclear microprobe data of particulate matter in EBC. The sizes and the elemental contents of particles suspended in EBC of workers of a lead processing industry and in EBC of non-exposed individuals were inspected. Results demonstrated that EBC of workers contain large aerosol particles, isolated and in agglomerates, contrasting with non-exposed individuals. The particles contained high concentrations of Cl, Ca, Zn and Pb that are elements associated to the production process. These elements were also present in the EBC matrix although in much lower levels, suggesting that a fraction of the inhaled particulate matter was solubilised or their size-ranges were below the nuclear microprobe resolution. Therefore, the morphological characterization of individual particles achieved with nuclear microprobe techniques helped describing EBC constituents in detail, to comprehend their origin and enabled to delineate methodological procedures that can be recommended in occupational assessments. These aspects are critical to the validation of EBC as a biomarker of exposure to metals for the respiratory system.     

Micro-fluidic target chamber machined by proton beam writing for the in situ analysis of gas absorption in synthetic crystals

Many synthetic crystals used for chemical and industrial applications have special internal structures, e.g. nano-pores, which allow separating different gases and fluids. Ion beam analytical methods can be used to study the gas diffusion and absorption in these materials in situ and to visualize their inner surfaces which affect these processes. For this purpose, a small target chamber was constructed in PMMA (polymethyl methacrylate) using proton beam writing (PBW). This micro-fluidic structure enables the establishment of a defined atmosphere around a crystal and allows the simultaneous ion beam analysis. In order to confine the gas from the high vacuum in the measurement chamber Si₃N₄-windows of 200 nm thickness were thermally bonded to the structured PMMA block yielding a closed target chamber with the possibility to accomplish PIXE and RBS measurements. In addition, two capillaries were connected to the chamber for gas inlet and evacuation. First tests showed that the construction is leak-proof and allows to establish a defined atmosphere. After that, the Argon gas diffusion into Zn(tbip)-crystals was studied. These measurements have shown unexpectedly high nickel concentrations in the host crystal which reduces the Argon density in these areas after absorption, because the Ni atoms decrease the pore size by replacing Zn-atoms in the Zn(tbip)-lattice. It could be demonstrated that gas diffusion and absorption in organic crystals can be studied in situ with high lateral resolution using ion beam analysis in a dedicated target chamber machined by PBW.     

颗粒物滤膜样品微量元素浓度的中子活化分析

用仪器中子活化分析技术分析了国际原子能机构（IAEA）组织的比对颗粒物滤膜盲样样品和标准参考物质NIST SRM－1633a样品。结果表明：比对的颗粒物滤膜样品的测定值与IAEA的参考标准值和所有参加比对的测定值的平均值相一致;质量检测标样的测定值与保证值符合良好;表明中子活化分析对测定样品中超微量、微量乃至常量元素的浓度是一种准确、可靠的方法。     

A microscopic and Synchrotron-based characterization of urban particulate matter (PM10-PM2.5 and PM2.5) from Athens atmosphere, Greece

Urban particulate matter (PM₁₀-PM_2.5 and PM_2.5) from Athens (Greece) atmosphere, primarily investigated by SEM-EDS, was further studied in the FLUO and SUL-X beamlines of ANKA Synchrotron facility (KIT, Germany). The SR μ-XRF study showed both geological (e.g. CaTi, CaK and CaSrKRb) and anthropogenic particles exhibiting heavy metal combinations such as FeCo, FeCoCuV and ZnV. It was also revealed that very hazardous metalloids and heavy metals, namely As and Pb, are concentrated in isolated respirable (PM_2.5) microparticles. It was attempted to investigate the oxidation state of As by means of μ-XANES. The As K-edge XANES spectrum of the sample shows a main peak at about 11.874 keV which matches adequately with the As(V) reference spectrum but part of the As seems to have a lower oxidation state (most probably As(III)). This is the first non-bulk study with regard to the partitioning and solid-state speciation of hazardous chemical elements in urban atmospheric microparticles from greater Athens area, rated as an alpha-world city with a population of ca. 4 million people.     

Experimental study on the parameter optimization and application of a packed-bed dielectric barrier discharge reactor in diesel particulate filter regeneration

To compensate for the shortcomings of the thermal and catalytic regeneration of the diesel particulate filter(DPF),a self-designed packed-bed dielectric barrier discharge(DBD)reactor for DPF regeneration was developed.The DBD reactor with the main active substance of nonthermal plasma(NTP)as the target parameter was optimized by adjusting the feed gas,packing particles(material or size),and cooling water temperature.Moreover,a set of optimal working parameters(gas source,O2;packing particles,1.2-1.4 mm ZrO2;and cooling water temperature,20℃)was selected to evaluate the effect of different O3 concentrations on DPF regeneration.The research results showed that selecting packing particles with high dielectric constant and large particles,as well as reducing the cooling water temperature,with oxygen as the feed gas,contributed to an increase in O3 concentration.During DPF regeneration,the following changes were observed:the power of the NTP reactor decreased to lower than 100 W,the O3 concentration increased from 15 g m-3 to 45 g m-3,the CO and CO2 volume fractions of the particulate matter decomposition products increased,and the peak regeneration temperature increased to 173.4℃.The peak temperature arrival time was 60 min earlier,indicating that the regeneration rate of DPF increased with the increase in O3 concentration.However,the O3 utilization rate(the amount of carbon deposit removed per unit volume O3)initially increased and then decreased;when the O3 concentration was set to 25 g m-3,the highest O3 utilization rate was reached.The packed-bed DBD technology contributed to the increase in the concentration of NTP active substances and the regeneration efficiency of DPF.It provides a theoretical and experimental basis for high-efficiency regeneration of DPF at low temperatures(＜200℃).     

Ion beam analysis of a structural phase transition in porous TiO2/V2O5 ceramics with rough surfaces

TiO₂/V₂O₅ based ceramic materials applied in catalysis were investigated. Structural properties like the grain diameter of these pressed ceramic powders were analysed by means of Rutherford backscattering (RBS) making use of an analytic model to describe the energy spectra of porous rough samples. Grain diameters of these samples were deduced as function of process temperature and chemical composition and related to a phase transition from the TiO₂-Anatase/V₂O₅-Shcherbinaite to Rutile solid solution (Rutile-ss) structure. RBS data were compared to results of scanning electron microscopy (SEM). The activation energy for the sintering at the phase transition was estimated to 5.4 eV.