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.     

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.     

PIXE and RBS analysis of Tl-1223 superconducting phase substituted by scandium

Ion beam analysis techniques (IBA) were performed to determine the elemental stoichiometry of superconducting samples of type TlBa₂Ca_2−xSc_xCu₃O_9−δ, with 0 ? x ? 0.6, prepared via solid-state reaction technique. By combining particle induced X-ray emission (PIXE) with Rutherford backscattering spectrometry (RBS), the stoichiometry of the samples is determined. However, the oxygen content is obtained by using non-Rutherford backscattering cross-section at 3 MeV proton beam. Furthermore, the prepared samples were also characterized using X-ray powder diffraction (XRD) and electrical resistivity measurements. The X-ray data indicate that the partial substitution of Ca²⁺ by Sc³⁺ ions does not affect the tetragonal structure of Tl-1223 superconducting phase. The superconducting transition temperatures T_c, determined from electrical resistivity measurements, was found to be highly correlated to the Sc-content.     

Assessment of DNA damage of Lewis lung carcinoma cells irradiated by carbon ions and X-rays using alkaline comet assay

DNA damage and cell reproductive death determined by alkaline comet and clonogenic survival assays were examined in Lewis lung carcinoma cells after exposure to 89.63 MeV/u carbon ion and 6 MV X-ray irradiations, respectively. Based on the survival data, Lewis lung carcinoma cells were verified to be more radiosensitive to the carbon ion beam than to the X-ray irradiation. The relative biological effectiveness (RBE) value, which was up to 1.77 at 10% survival level, showed that the DNA damage induced by the high-LET carbon ion beam was more remarkable than that induced by the low-LET X-ray irradiation. The dose response curves of “Tail DNA (%)” (TD) and “Olive tail moment” (OTM) for the carbon ion irradiation showed saturation beyond about 8 Gy. This behavior was not found in the X-ray curves. Additionally, the carbon ion beam produced a lower survival fraction at 2 Gy (SF2) value and a higher initial Olive tail moment 2 Gy (OTM2) than those for the X-ray irradiation. These results suggest that carbon ion beams having high-LET values produced more severe cell reproductive death and DNA damage in Lewis lung carcinoma cells in comparison with X-rays and comet assay might be an effective predictive test even combining with clonogenic assay to assess cellular radiosensitivity.     

Swift heavy ion irradiated InGaAs/InP multi quantum wells: Band-structure, interface and surface modifications

The band-structure, interface and surface modification by swift heavy ion irradiation of In_0.55Ga_0.45As/InP multi quantum wells have been studied using photoluminescence, high resolution X-ray diffraction and atomic force microscopy. Three distinct photoluminescence peaks were observed for as-grown samples at low temperature and at room temperature the peaks merge together. Detailed analysis has been carried out to understand the origin of additional satellite peaks. A peak shift of about 23 nm was observed for irradiated samples after annealing. Highly-ordered satellite peaks were observed in X-ray scans of as-grown and Ag ion irradiated samples. In comparison, Au ion irradiated sample showed stronger interfacial degradation as seen by the diminished satellite peaks. The peak position of the irradiated samples shifted to the compressive side and was broadened in comparison with as-grown samples. The as-grown and annealed samples show smooth surfaces whereas irradiation results in nano-sized dot/island types of structures at the surface. The results are discussed in the light of complementary information provided by these techniques.     

PIXE identification of fine and coarse particles of aerosol samples and their distribution across Beirut

This study is the first national attempt to assess the levels of PMs in Beirut city and consequently understand air pollution distribution. Aerosol sampling was carried out using three PM₁₀ and three PM_2.5 samplers which were installed at three locations lying along the SE-NW direction over Beirut. The sampling of PM₁₀ and PM_2.5 was done during a period extending from May till December 2009. The random collection of the particles (1 in 6 days) was carried out on Teflon filters, for a period of 24-h. The elemental analysis of particulate matter was performed using proton induced X-ray emission technique PIXE at the Lebanese 1.7 MV Tandem-Pelletron accelerator of Beirut. Na, Mg, Al, Si, P, S and Cl were quantified using 1 MeV proton beam, while K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn and Pb were determined using 3 MeV-energy of proton beam.     

Characterization and applications of a new tabletop confocal micro X-ray fluorescence setup

A tabletop confocal three-dimensional micro X-ray fluorescence (3D micro-XRF) setup was designed, based on polycapillary X-ray optics and a micro-focus X-ray source. This confocal setup consists of a polycapillary full lens to focus the incident beam and a polycapillary half lens to collect the X-ray fluorescence. The confocal volume was proved to be ellipsoidal. The full-width at half maximum (FWHM) of the confocal volume in three directions were measured with a “knife edge” scan method to obtain the spatial resolution of the confocal setup. The structure of multilayer samples was studied using the depth scan technique.     

Identification of origin of single aerosol particles using polycapillary X-ray lens

A micro X-ray fluorescence (Micro-XRF) spectrometer based on a polycapillary focusing X-ray lens (PFXRL) and a laboratory X-ray source was designed to carry out the XRF analysis of single aerosol particles. The minimum detection limit (MDL) of this Micro-XRF spectrometer was 9 ppm for the Fe-Kα. The percentage of the particles of vehicle exhaust among aerosol particles was studied in Beijing, Chinese capital, during the test of odd-even driving restrictions for Beijing 2008 Olympics Games. This Micro-XRF spectrometer had potential applications in the analysis of single aerosol particles.     

Synthesis of nanodimensional TiO2 thin films using energetic ion beam

Nanophases of TiO₂ are achieved by irradiating polycrystalline thin films of TiO₂ by 100 MeV Au ion beam at varying fluence. The surface morphology of pristine and irradiated films is studied by atomic force microscopy (AFM). Phase of the film before and after irradiation is identified by glancing angle X-ray diffraction (GAXRD). The blue shift observed in UV-vis absorption edge of the irradiated films indicates nanostructure formation. Electron spin resonance (ESR) studies are carried out to identify defects created by the irradiation. The nanocrystallisation induced by SHI irradiation in polycrystalline thin films is studied.     

The micro-imaging station of the TopoTomo beamline at the ANKA synchrotron light source

The TopoTomo bending magnet beamline at the ANKA synchrotron facility in Karlsruhe (Germany) operates in the hard X-ray regime (above 6 keV). Recently, an X-ray micro-imaging station has been installed at TopoTomo. For typical imaging applications, a filtered white beam or from 2009 on a double-multilayer monochromator is used. In order to optimize the field of view and the resolution of the available indirect pixel detectors, different optical systems have been installed, adapted, respectively, to a large field of view (macroscope) and to high spatial resolution (microscope). They can be combined with different camera systems, ranging from 14-bit dynamic range CCDs to fast CMOS cameras. The spatial resolution can be brought substantially beyond the micrometer limit by using a Bragg magnifier. Due to the moderate flux of the beamline compared to insertion-device beamlines on third generation light sources, special emphasis has been put on the efficiency of the detectors via a dedicated scintillator concept. The layout of the beamline optics makes optimal use of the coherence properties. Thus, absorption contrast, phase-contrast and analyzer-based imaging can be applied. Additionally, white beam synchrotron topography is performed, using digital indirect X-ray pixel detectors as well as X-ray film.     

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.     

Synthesis of uranium nitride by a mechanically induced gas-solid reaction

A high energy, low-temperature, ball-milling route was used to directly produce uranium nitride. Pure uranium metal particles (∼100 μm) were ball milled under a 420 kPa nitrogen atmosphere for 24 h at ambient temperature to yield phase pure U₂N₃ powder as confirmed by X-ray diffraction and energy dispersive spectroscopy. The median particle size was measured to be approximately 6 μm.     

VUV processing of polymers: Surface modification and deposition of organic thin films

N-rich organic surfaces have been obtained by means of vacuum ultraviolet (VUV) processing, via the functionalization of low-density polyethylene (LDPE) surfaces and also by polymerization of hydrocarbons (CH₄ and C₂H₄) mixed with ammonia (NH₃). The fundamental mechanisms involved in grafting reactions, as well as in the polymerization of these binary mixtures are discussed as a function of wavelength, λ, of the VUV sources. The surface compositions and deposition rates are characterized by X-ray photoelectron spectroscopy (XPS) and by UV-vis spectroscopic ellipsometry, respectively. We show that photochemical reactions can be optimized by judiciously selecting λ of the VUV source, so that maximum absorption and photo-dissociation can be achieved.     

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.     

Effect of swift heavy ion irradiation on nanocrystalline CaS:Bi phosphors: Structural, optical and luminescence studies

Luminescence studies of CaS:Bi nanocrystalline phosphors synthesized by wet chemical co-precipitation method and irradiated with swift heavy ions (i.e. O⁷⁺-ion with 100 MeV and Ag¹⁵⁺-ion with 200 MeV) have been carried out. The samples have been irradiated at different ion fluences in the range 1 × 10¹²-1 × 10¹³ ions/cm². The average grain size of the samples before irradiation was estimated as 35 nm using line broadening of XRD (X-ray diffraction) peaks and TEM (transmission electron microscope) studies. Our results suggest a good structural stability of CaS:Bi against swift heavy ion irradiation. The blue emission band of CaS:Bi³⁺ nanophosphor at 401 nm is from the transition ³P₁ → ¹S₀ of the Bi³⁺. We have observed a decrease in lattice constant (a) and increase of optical energy band gap after ion irradiation. We presume this change due to grain fragmentation by dense electronic excitation induced by swift heavy ion. We have studied the optical and luminescent behavior of the samples by changing the ion energy and also by changing dopant concentration from 0.01 mol% to 0.10 mol%. It has been examined that ion irradiation enhanced the luminescence of the samples.     

Ion beam induced modifications in electron beam evaporated aluminum oxide thin films

Al₂O₃ thin films find wide applications in optoelectronics, sensors, tribology etc. In the present work, Al₂O₃ films prepared by electron beam evaporation technique are irradiated with 100 MeV swift Si⁷⁺ ions for the fluence in the range 1 × 10¹² to 1 × 10¹³ ions cm⁻² and the structural properties are studied by glancing angle X-ray diffraction. It shows a single diffraction peak at 38.2° which indicates the γ-phase of Al₂O₃. Further, it is observed that as the fluence increases up to 1 × 10¹³ ions cm⁻² the diffraction peak intensity decreases indicating amorphization. Surface morphology studies by atomic force microscopy show mean surface roughness of 34.73 nm and it decreases with increase in ion fluence. A strong photoluminescence (PL) emission with peak at 442 nm along with shoulder at 420 nm is observed when the samples are excited with 326 nm light. The PL emission is found to increase with increase in ion fluence and the results are discussed in detail.     

Chemical shift measurements of chlorine K X-ray spectra using a high-resolution PIXE system

A high-efficiency high-resolution wavelength-dispersive spectrograph with a von-Hamos configuration was developed for chemical state identification of elements in environmental samples using PIXE analysis. To evaluate the performance of this system, chlorine K X-ray spectra for NaCl, NH₄Cl and polyvinylchloride (PVC) targets were measured and compared. Also, to study the applicability to environmental mixed samples, mixtures of NaCl and NH₄Cl with different mixing ratios were measured. Through observation of Cl Kα₁ X-ray from NaCl, the energy resolution of the system was determined to be 1.1 eV. For the NaCl sample, a Kβ_x line was observed at an energy, which is higher than that of the Kβ main peak by 2 eV, whereas no Kβ_x emission was observed for the NH₄Cl sample. The chemical shift of the Kβ main peak for PVC relative to that for NaCl was about 1.2 eV. For NaCl-NH₄Cl mixture targets, the relative intensity of Kβ_x satellite to the Kβ main line provided an indication of mixing ratio. Energies and relative intensity of Cl Kβ X-ray satellites for NaCl and NH₄Cl samples calculated by a simple molecular-orbital method agreed only qualitatively with the experimental results.     

Preparation and characterization of Ag-coated cenospheres by magnetron sputtering method

In this paper, we show the feasibility of the magnetron sputtering deposition technique to grow 10-100-nm thick, uniform, continuous and well adhesive silver films on cenosphere particles so that the properties of the core particles can be suitably modified. Experiments were conducted with a magnetron sputtering deposition system in which a newly designed sample stage equipped with an ultrasonic vibration generator was used for the tumbling of cenosphere particles. The cenosphere particles are characterized by X-ray diffraction (XRD) analysis, field emission scanning electron microscope (FE-SEM) and inductively coupled plasma-atom emission spectrometer (ICP-AES) before and after the coating process. All results show the metal film has been successfully coated onto cenosphere particles. Under the given conditions, up to 3.0 wt.% silver was deposited on cenosphere particles measured by ICP-AES. The FE-SEM results indicate that at the micro-scale the relatively uniform, compact and well adhesive silver films with about 51 nm thickness were successfully deposited on cenosphere particles. The XRD analytic result indicates that the nanometer metal film has a face-centered cubic structure.     

Effect of swift heavy ion irradiation on hydrothermally synthesized hydroxyapatite ceramics

The effect of swift heavy ion irradiation on hydroxyapatite (HAp) ceramic - a bone mineral was investigated. The irradiation experiment was conducted using oxygen ions at energy of 100 MeV with three different fluences of 10¹², 10¹³, 10¹⁴ ions/cm². The irradiated samples were characterized by glancing angle X-ray diffraction (GXRD), atomic force microscopy (AFM), dynamic light scattering (DLS), photoluminescence spectroscopy (PL), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX). GXRD confirmed incomplete amorphisation of HAp with increase in fluence. There was considerable reduction in particle size on irradiation leading to nanosized HAp (upto 53 nm). PL studies showed emission in the visible wavelength region. The irradiated samples exhibited better bioactivity than the pristine HAp.     

Development of a novel reaction chamber for ion beam analysis of large samples

A novel vacuum chamber for ion beam analysis of large-size industrial samples - whose analysis are not feasible in conventional ion beam analysis reaction chambers - has been designed, fabricated and successfully tested. Using the newly developed chamber, both PIXE and RBS analyses could be carried out at the same time and on the same point of the samples. Ion beam analysis using this novel chamber lacks the disadvantages of external beam analysis and benefits the advantages of in-vacuum analysis. This has been achieved by designing a tiny open port in the wall of the reaction chamber to be sealed with a small flat area of sample body where its analysis is of interest. As a case study, two samples of gas turbine blades, a corroded one at highly corrosive environment and a refurbished one after application of certain coatings are analysed using the novel chamber. Experimental results confirm the performance and capability of the reaction chamber.