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.     

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.     

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.     

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.     

用碳稳定同位素估算大气细颗粒物中多环芳烃的来源

建立了用碳稳定同位素比估算大气颗粒物中多环芳烃（PAHs）的方法,该方法包括二氯甲烷提取、薄层色谱纯化和气相色谱-燃烧系统-同位素质谱测定碳稳定同位素组成(δ¹³C);并用该方法对上海市大气颗粒物PM_2.5中PAHs的来源进行估算。结果表明:采样点PM_2.5中PAHs的δ¹³C值随着分子量的增加而减小;与潜在污染源中相应值相比,更接近于燃煤和生物质燃烧的相应值,表明采样点处PM_2.5中的PAHs受燃煤和生物质燃烧的影响大于机动车尾气。PAHs来自燃煤、机动车尾气和生物质的贡献分别为3%-21%、29%-33%和46%-67%。这一结果与采样点的特殊环境一致,表明碳稳定同位素比能够定量估算大气细颗粒物中PAHs的来源。     

大气颗粒物PM10和PM2.5元素组成的中子活化分析

在北京市郊区设立采样点，使用Gent采样器收集PM₁₀（直径小于10μm）和PM_2.5（直径小于2.5μm）大气颗粒物。利用仪器中子活化分析（INAA）法对2005年春、夏两季采集的样品进行测量，用k₀法中子活化分析（ADVNAA软件）对元素含量进行定量计算，得出春季PM_2.5平均浓度为41.43μg/m^₃，PM₁₀平均浓度为140.82μg/m³；夏季PM_2.5平均浓度为50.63μg/m³，PM₁₀平均浓度为119.10μg/m³。通过分析可以看出，样品中污染元素随季节、气象条件变化，并通过富集因子来寻找污染元素的来源。[JP]     

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.     

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.     

Elemental analysis of limestone samples from Ewekoro limestone deposit in southwest Nigeria

Limestone samples of different colours from Ewekoro limestone deposit in Ogun State, Nigeria were subjected to elemental analysis by proton-induced X-ray emission (PIXE) and proton-induced gamma-ray emission (PIGME) techniques. The irradiation was by 2.5 MeV proton beams from the ion beam analysis (IBA) facility of the 3 MV Van de Graaff accelerator at the Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights. Elemental composition and concentrations of 22 major, minor and trace elements were determined. The NIST geological standard, NBS278, was analysed for quality assurance. The concentrations of the major elements (Ca, Fe, K and Al) are similar in the samples while the other major elements differed. Calcium accounts for about 38%, giving 86.8% CaCO₃ content in the limestones. The major elements (Al, Ca, Fe, Si, S and K), present in the limestones, were also found to be enriched in airborne particulate matter studied by earlier workers, thus confirming cement dust as the major contributor to the particulate matter within and around cement factories.     

Detailed mass size distributions of atmospheric aerosol species in the Negev desert, Israel, during ARACHNE-96

As part of the 1996 summer intensive of the Aerosol, RAdiation and CHemistry Experiment (ARACHNE-96), the mass size distribution of various airborne particulate elements was studied at a remote site in the Negev Desert, Israel. Aerosol collections were made with 8-stage PIXE International cascade impactors (PCIs) and 12-stage small deposit area low pressure impactors (SDIs) and the samples were analyzed by PIXE for about 20 elements. The mineral elements (Al, Si, Ca, Ti, Fe) exhibited a unimodal size distribution which peaked at about 6 μm, but the contribution of particles larger than 10 μm was clearly more pronounced during the day than during night. Sulphur and Br had a tendency to exhibit two modes in the submicrometer size range, with diameters at about 0.3 and 0.6 μm, respectively. The elements V and Ni, which are indicators of residual fuel burning, showed essentially one fine mode (at 0.3 μm) in addition to a coarse mode which represented the mineral dust contribution. Overall, good agreement was observed between the mass size distributions from the PCI and SDI devices. The PCI was superior to the SDI for studying the size distribution in the coarse size range, but the SDI was clearly superior for unravelling the various modes in the submicrometer size range.     

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。     

Detection of non-sea salt sulphate aerosol at a remote coastal site in South Africa: A PIXE study

An aerosol sampling site based on a single-stage streaker sampler with four-hour time resolution was established in 1993 at Brandt-se-Baai, on the north-western coast of South Africa (31.5°S 18°E, 50 m asl). The site was deployed to monitor the generation of dust from the local mining operations and in part to test the hypothesis of large-scale air mass recirculation over Southern Africa. Streaker samples were analysed by PIXE for the usual crustal derived elements and sulphur. Sulphate aerosols over southern Africa are produced in the atmosphere by oxidation of SO₂, from industry, or DMS, from the ocean. Industrial related sulphate plays a key role in tracing long-range transport of anthropogenic pollutants.

We present results from selected monthly samples collected during 1996. Measured particulate sulphur has been apportioned between contributions from sea spray and non-sea salt sulphate (NSS) aerosols. Marine particulate sulphur, present in the regional background, was traced by its correlation with Na and Cl, which were routinely detected. The NSS content of these air masses was enriched with respect to the expected sea salt sulphur by two orders of magnitude. Al, Si, K, Ca, Ti and Fe, the major crustal elements, were measured only episodically with the occurrence of strong south-easterly winds. These winds are associated with wind blown dust from a mine located 4 km from the site.

These results are the first direct aerosol characterisation of the remote region of the western seaboard of southern Africa. Specifically the sulphur measurements at this site provide insights into relative contributions of natural DMS, industrial and sea salt contributions of particulate sulphate.     

M-shell X-ray production cross sections for PIXE applications

M-shell X-ray production cross sections by protons of energies 0.1–4.0 MeV are reported for the most intense M_β(M_4,5N_6,7), M_γ(M₃N_4,5) and M₃O_4,5 M-X ray transitions appearing in PIXE spectra. The cross sections have been measured systematically for selected heavy elements between Ta and Th (Z₂=73–90). Measured M-X-ray production cross sections were found to be universal with respect of M-shell scaled velocity ξ_M. The data are compared with available theoretical calculations of M-shell ionization by charged particles based on the plane-wave Born approximation (PWBA) and the semiclassical approximation (SCA), as well as the ECPSSR theory and relativistic RPWBA-BC which are going beyond the first order treatment. Simple parameterization of experimental proton induced M-X-ray cross sections is proposed for PIXE applications. This parameterization, being accurate within ±5%, can be used for precise determination of heavy metal concentrations by PIXE technique.     

GIC4117串列加速器外束PIXE/PIGE分析系统

本文介绍在北京师范大学GIC4117串列加速器上建立的外束PIXE/PIGE分析系统,和基于此系统的薄样品外束PIXE/PIGE定量分析方法。给出了2010年Teflon滤膜采集的361个气溶胶样品外束PIXE分析得到的各元素平均探测限和最低探测限,并同真空PIXE分析探测限进行了比较。利用标准样品给出了激发曲线不同坪区薄样品外束PIGE分析F和Na的探测限,通过测定¹⁹F(p, p′γ)¹⁹F激发的197 keV γ射线得到的F的探测限可达73.9 ng•cm^-2,Na的探测限可达198.9 ng•cm^-2。     

PESA as a complementary tool to PIXE at CTU Prague

Proton Elastic Scattering Analysis (PESA) is a simple convenient method for hydrogen analysis in thin samples. A Proton Induced X-ray Emission (PIXE) target chamber was equipped with a PIPS detector for detection of forward-scattered protons. One of the objectives was to perform PIXE and PESA analyses of air particulate targets simultaneously. Tests and calibrations were fulfilled mainly with Mylar foils 1.5–6.5 μm thick in the proton energy region between 1.35 and 2.3 MeV. The energy dependence of scattering cross section is different from the Rutherford formula. Comparison of PIXE/PESA analysis with the Guelph Scanning Proton Microprobe Laboratory at the University of Guelph, Canada on seven aerosol samples was carried out. The intercomparison results validated our PESA/PIXE quality assurance protocol. In addition, repeated measurements of Gelman Teflo^TM filters indicated a gradual increase of hydrogen content by 1 ng/cm² per 1 μC/cm² proton dose.     

Aerosol characterisation in Italian towns by IBA techniques

The composition of particulate matter in the atmosphere of four major Italian towns (Florence, Genoa, Milan and Naples) has been studied with the extensive application of IBA techniques. The aerosol has been collected simultaneously in the four towns during the first weeks of year 2001, by two-stage continuous streaker samplers, which provide the separation of the particulate matter in two fractions. The concentrations in air of about 20 elements, and the total particulate mass, have been extracted in the PM2.5 and PM10 fractions with hourly resolution by PIXE, PIGE and optical analyses of about 2700 samples. IBA analyses have been performed at the 3 MeV external proton beam of the INFN accelerator facility at the University of Florence.     

Characterization of ancient Chinese pottery decorated with a black pigment

The Yangshao type pottery, made about 6000 yrs ago, was investigated by X-ray diffraction (XRD), and confirmed to be composed of quartz, feldspar, muscovite and calcite. A black pigment on it was assumed to be (Mn, Fe)₃O₄ from Particle Induced X-ray Emission (PIXE) and XRD experiments. Firing temperature of the pottery was assumed to be less than 600°C from a heating experiment of the fragment of the pottery.     

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.     

Industrial aerosol characterisation at a remote site in South Africa

South Africa is the most industrialised country in southern Africa with approximately 1.1 Tg of sulphur emitted from anthropogenic activities per annum. Complex circulation patterns and highly stable vertical atmospheric conditions promote the accumulation of pollutants below 700 hPa or 3000 m asl. A remote site in the Eastern Cape of South Africa, Ben Macdhui (30.5°S 27.9°E, 3001 m) was selected for testing the hypothesis that industrial emissions, specifically sulphate, are transported over thousands of kilometres in anticyclonic type patterns of flow and exported from the subcontinent towards the Indian Ocean at about 30°S. Time resolved particulate sampling (streaker) was conducted between June 1995 and January 1997. To characterise the industrial aerosol signal, two intensive sampling campaigns (summer and winter) were undertaken in 1996. Aerosol samples were collected by a streaker sampler and an open-faced stacked filter unit (SFU). Samples were PIXE analysed to obtain elemental concentrations. The industrial signature detected at Ben Macdhui was characterised by elevated concentration of sulphur and iron in the fine fraction and fine sulphur detected in the coarse mode. Other sources identified from the elemental data were soil (Al, Si, Ca, Mg, K, S, Mn), biomass burning (fine K) and marine (Cl, Ca, Mg, S and coarse K). These four sources accounted for approximately 70% of the total detected elemental mass. Major individual contributions came from the crustal (53%) and industrial components (21%). Air parcel trajectory analyses confirmed that peak episodes of enhanced aerosol sulphur were related to transport from the industrial Highveld region of South Africa and conversely that clean air masses originated over the southern oceans.     

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.