Elemental composition of size-fractionated urban aerosol collected in Florence, Italy; preliminary results

An extensive investigation is in progress aiming at the characterisation of the air particulate composition in Florence. We present here the preliminary results concerning the analysis of size-fractionated aerosol samples taken by two-stage streaker samplers in two sites characterised by different urban settings (one in a heavy traffic area, one in a green area). The sampling period (21 January–22 February) includes two days during which the Municipality of Florence has banned the circulation of non-catalytic cars, due to the increase of NO₂ above the “recommended safety values”. Hourly concentrations of 20 elements from Na to Pb were determined using the external beam PIXE facility of the I.N.F.N. Van de Graaff accelerator at the Physics Department of the Florence University. Factor analysis on the data set confirms that traffic is the main source of atmospheric pollution in Florence. The ban of non-catalytic cars seems to have produced no effect on the concentration of detected elements (in particular Pb and Br).     

PIXE and XRF analysis of particulate matter samples: an inter-laboratory comparison

PIXE and XRF are very effective techniques in atmospheric aerosol investigation, therefore they are extensively used by the authors. In this work an inter-laboratory comparison of the results obtained analysing several samples (collected on different substrata) with both techniques is presented: the samples were analysed by PIXE (in Florence, at the 3 MV Tandetron accelerator of LABEC laboratory) and by XRF (in Genoa and Milan, where two Oxford XRF instruments are operational). The results of the three sets of measurements are in good agreement for all the analysed samples.The aim of this work was also to compare PIXE and XRF performance in atmospheric aerosol analysis with the routine set-up currently in use at the three laboratories, to determine the best technique to be applied depending on the substratum used for aerosol sampling and the main elements of interest for each specific research project. Results of the comparison between the minimum detection limits of both techniques will be shown for all the measured elements, for different substrata (Teflon, polycarbonate and cellulose mixed esters).     

Fundamental studies on extraction of actinides from spent fuels using liquefied gases – Conversion of copper into nitrate with NO2 and extraction of Nd(III) nitrate by CO2 with TBP

The nitrate conversion with liquefied NO₂ and the nitrate extraction with SC-CO₂ were demonstrated for copper powder and neodymium nitrate instead of actinide compounds. Copper contacted with NO₂ in an autoclave at 353 K changed to water-soluble compounds. By XRD analysis of the product in the atmospheric condition, the formation of copper nitrate hydrate (Cu(NO₃)₂·2.5H₂O) was confirmed. As for the extraction, neodymium nitrate loaded in an autoclave was successfully extracted with the fluid of TBP and SC-CO₂ at 15 MPa, 313 K.     

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.     

多种离子束分析技术在大气气溶胶研究中的应用

介绍了使用质子弹性散射测定大气气溶胶样品中的氢，使用质子透射能量损失测定样品的总质量和使用质子X荧光测定采在不同滤膜上的气溶胶样品化学成分的分析方法。结果表明，多种离子束分析技术的组合使用，为大气气溶胶研究提供了十分重要和有用的工具。     

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.     

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.     

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.     

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.     

Air quality work at Guelph: GAViM and a traffic tunnel study

The Guelph Aerosol and Visibility Monitoring (GAViM) program presently runs three monitoring sites: two rural sites compatible with the IMPROVE protocol and one urban site mostly for special comparison studies. Fine aerosol is analyzed by the Laser Integrated Plate Method (LIPM), Proton Elastic Scattering Analysis (PESA), Proton Induced X-ray Emission (PIXE) and gravimetric analysis. Air quality data from the presently running sites and from two rural sites operated in the past are available through the WWW. The Guelph Scanning Proton Laboratory also participates in other aerosol programs: PIXE was employed to determine the composition of the ambient aerosol in a Vancouver traffic tunnel, to identify the main emission sources and to make estimates of vehicle emission factors. The PIXE facility was also modified for analysis of size-fractionated samples from the PIXE International Cascade Impactor (PCI) sampler. Significant improvement in detection limits for light elements due to the two-detector PIXE system used in Guelph, was justified particularly because of low air particulate loadings in case of PCI.     

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.     

PIXE as a complement to trace metal analysis of sediments by ICP-OES

The adverse effects of metal contamination in sediments require methods that can quickly and accurately assess the extent of environmental pollution. Particle induced X-ray emission spectrometry (PIXE) is demonstrated to be a viable alternative to an established method, which consists of acid digestion and Inductively coupled plasma-optical emission spectrometry (ICP-OES) to measure trace metals in sediment. The analysis of trace metal composition by both techniques on a NIST Standard Reference Material mud gives results that are consistent with the certified values for fourteen measured metals, seven of which are common to both methods. A comparison study conducted on a sediment core from a freshwater lake with a known chromium contamination in Muskegon County, MI also shows a good correlation between the methods for transition metals of environmental interest over a wide range of metal concentrations. Total sample preparation and analysis time for the PIXE measurements is roughly one third that of acid digestion and ICP-OES. Also, the acid digestion step does not elute all the metal, while the nondestructive PIXE approach is a total metals analysis method. However the PIXE method generally has higher limits of detection for many environmental metal contaminants. By combining the two techniques, the acid digestion elution factor can be quantified by running PIXE on an original sample and on the residue resulting from acid digestion.     

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.     

Analysis of C, N and O in aerosol collected on an organic backing using internal blank measurements and variable beam size

A method with low MDL (minimum detection limit) was developed for analysis of carbon (C), nitrogen (N) and oxygen (O) in aerosol samples collected on an organic backing. An accelerator-produced beam of protons interacting with the sample and the detection of elastically scattered protons (PESA; particle elastic scattering analysis) and emitted X-rays (PIXE; particle-induced X-ray emission) were the basic components of the setup. The method is based on measurement of internal blank concentrations, i.e. measurement of the blank concentration outside the aerosol deposit in each sample, and the use of two sizes of the beam in order to improve the MDL of the analysis. Large beam size covering the entire aerosol deposit was used to obtain quantitative analysis with PIXE. Small beam was used to obtain relative elemental concentrations with PESA and PIXE, which were transformed to absolute values by the aid of large-beam analysis. The small-size-beam served two purposes: to make internal blank measurements feasible and to improve the signal ratio of aerosol-deposit to backing. Compared with the traditional way of analysis, using a beam that is larger than the deposit and specially prepared blank samples, the new method reduced the MDL of C, N and O by a factor of 130, 70 and 90, respectively. The new method was applied to aerosol samples collected in the upper troposphere and the lowermost stratosphere from the CARIBIC platform. As far as the authors know, these measurements are the first quantitative determinations of C, N and O in the aerosol of this part of the atmosphere. The results show that these elements together with sulfur are major components of the aerosol.     

Analysis of sulphur with external beam proton induced gamma-ray emission analysis

Applicability of the ³²S(p, p′ γ)³²S reaction for sulphur analysis as a complementary method to PIXE has been investigated. The optimum energy region for the bombarding protons has been determined for both thick samples and for thin atmospheric aerosol samples. By optimizing the external beam method, sulphur concentrations at the 100 ppm level for thick organic samples and at the 100 ng/cm² level for aerosol samples are detectable.     

Characterisation of ferromagnetic magnetic storage media surfaces by complementary particle induced X-ray analysis and time of flight-energy dispersive elastic recoil detection analysis

Thin (10 nm–1 μm) films of ferromagnetic material constitute an important class of materials that are difficult to analyse by conventional ion beam analytical (IBA) techniques because they are based on the ferromagnetic elements (Co, Fe, Mn, Ni, and Cr). The similar or overlapping isotope masses makes it difficult to separate the elemental signals using time of flight and energy dispersive elastic recoil detection (ToF-E ERD). In this exploratory study we have investigated the use of Particle Induced X-ray Emission (PIXE) measurements to refine the mass dispersive depth profile information from ToF-E ERD. The surfaces of two commercial magnetic media were investigated. One sample was a double density diskette with a coating of ferrite particles in an organic binder. The other sample was a complex C/Co/Cr/Ni–P/Al multilayer structure taken from a standard hard disc. The Lund nuclear microprobe with a 2.55 MeV proton beam was used for PIXE analysis. ToF-ERD measurements were carried out using a 55 MeV ¹²⁷I¹⁰⁺ ion beam incident at 67.5° to the surface normal. The time of flight and kinetic energy of recoils ejected at 45° to the ion beam direction was measured in a detector telescope. The findings demonstrate that by detailed analysis of the PIXE spectra it is possible to remove the ambiguities in mass assignment of the ToF-ERD data associated with the ferromagnetic elements.     

Use of the nuclear microprobe at the University of Arizona for the study of heavy metal deposition in rabbit renal tissue

Industrial wastes consigned to disposal sites frequently contain substantial amounts of heavy metals. We have successfully applied proton induced X-ray emission analysis (PIXE) in the conduct of heavy metal (Hg, Cd, Cr, As) toxicity studies using precision cut rabbit renal cortical slices. The large beam diameter (4000 μm) of the proton macroprobe at The University of Arizona Ion Beam Analysis facility allowed an overall concentration of the metal(s) of interest in the samples to be determined, but lacked the ability to resolve point concentrations in the tissue. The ability to locate these areas has now been made available to us with the addition of a rastering microprobe (μ-PIXE) to the facility. Studies now being conducted in our laboratory using this micro-technique include analysis of renal tissue taken from rabbits injected intraperitoneally with HgCl₂, K₂Cr₂O₇, and NaAsO₂. The small beam size (3 μm) and the ability to raster this beam over areas of up to 125 μm × 125 μm has allowed regional mapping of endogenous and non-endogenous metal concentrations and revealed trends in heavy metal deposition in in vivo treated renal tissue, significantly increasing the amount of information obtained from these animal studies using PIXE alone. The combination of small beam size, high resolution, and multi-element detection makes μ-PIXE a powerful tool for investigating the impact of non-endogenous metals on the kidney.     

甲基膦酸二甲庚酯对Zr(Ⅳ)的萃取行为

以正十二烷为稀释剂,研究了甲基膦酸二甲庚酯(DMHMP)萃取剂对硝酸介质中Zr(Ⅳ)的萃取性能。从3.0 mol/L HNO₃中萃取Zr(Ⅳ)的分配比与萃取剂浓度及硝酸根浓度的关系表明：萃取过程中DMHMP以中性萃取剂形式与Zr(Ⅳ)配位,萃取反应方程式主要为： Zr⁴⁺+2DMHMP+4NO^-₃=Zr(NO₃)₄·2DMHMP 随着硝酸浓度的增大,还会生成Zr(NO₃)₄·2DMHMP·2HNO₃和Zr(NO₃)₄·2DMHMP·3HNO₃。该反应为放热反应,降低温度有利于DMHMP对Zr(Ⅳ)的萃取。     

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.