Elemental characterization of airborne particles in Khartoum,Sudan

The aim of this study was to investigate the elemental composition of airborne particles in the Khartoum area, particularly small inhalable particles of diameter ≤10 µm. Aerosol particles were collected during the period April–May 2001. The sampling was done using a dichotomous virtual impactor capable of separating airborne particles <2.5 µm in a fine mode and 2.5–10 µm particles in a coarse mode. Energy‐dispersive x‐ray fluorescence analysis was used to determine the elemental concentrations of 14 elements in the samples. Concentrations of black carbon were also measured on the two size fractions. The results obtained were compared with previous data from Khartoum and other African locations. Si, K, Ca, Ti, Mn, Fe, Zn and Sr were found to be dominant in the collected particulates. Day period collections were found to have higher elemental concentrations than those of night periods. This is attributed to higher traffic levels and wind speeds. The results show that dust aerosol transport and resuspension are the main sources that affect the quality of ambient air in the Khartoum area. The elemental concentrations from anthropogenic sources are generally low. Copyright © 2004 John Wiley & Sons, Ltd.     

Elemental content of aerosol particles in an underground tram station

Particulate matter is an important air pollutant, especially in closed environments like a tunnel. The aim of this study was to determine the mass, black carbon, and elemental concentrations of particulate matter of two size fractions at an underground tram station in Hammarkullen, Gothenburg, Sweden. Samples were collected during June 2007 using a dichotomous virtual impactor separating the sampled aerosol particles into coarse (PM_(2.5–10)) and fine (PM_2.5) fractions. To minimize the possible influence of waiting passengers, the platform for trams going towards the suburb Angered was chosen. The elemental analysis of the samples, collected on Teflon filters, was carried out using energy dispersive x‐ray fluorescence (EDXRF) spectrometry, resulting in concentrations of 14 elements in most of the samples. Principal component analysis (PCA) was applied to identify possible sources for the elements in the particles. Owing to the tunnel environment, the elemental difference between the fine and coarse particle fractions was not as large as that in similar particles collected under normal outdoor ambient conditions. Likewise, the influence of the local weather situation was not significant. Particle content from the tram traffic was identified by PCA, with Fe being the major element in both coarse and fine particles. The particle mass concentration was higher in the tunnel compared to the ambient concentration at the monitoring station Femman in downtown Gothenburg. In some days, the mass concentration exceeded the Swedish daily ambient air quality standard of 50 µg m^?3, but it was lower than the limits in the environmental work act, 5 mg m^?3. Copyright © 2009 John Wiley & Sons, Ltd.     

Evaluation of the concentration of chemical elements in suspended particulate matter inside a small bronze and iron foundry industry,using a streaker sampler and EDXRF

The aim of this study was to determine and evaluate the temporal profiles of the concentration of chemical elements in the suspended particulate matter present inside a small bronze and an iron foundry industry. To collect the samples, we used a streaker sampler that separates particles with aerodynamic diameters smaller than 10 µm (PM₁₀) in two fractions: fine (particles with aerodynamic diameters less than 2.5 µm; PM_2.5) and coarse (between 2.5 µm and less than 10 µm; PM_10–2.5). The collection of samples was taken every 20 min during a total time of 8 and 5 h of molding and casting of bronze and iron, respectively. The samples collected in the form of strips on a filter (fine fraction) and an impactor (coarse fraction) were analyzed by the energy dispersive X‐ray fluorescence technique. In the excitation, an X‐ray tube with Mo target and Zr filter was used, operated at 30 mA/30 kV. For detecting the characteristic of X‐rays, a semiconductor Si(Li) detector was used, coupled to a multi‐channel spectrometer, with a 300 s excitation/detection time. The results of the temporal profiles of chemical element concentrations in coarse and fine fractions were discussed and compared with the maximum levels set by the Brazilian and international environmental agencies. Copyright © 2013 John Wiley & Sons, Ltd.     

Chemical composition and mass closure for PM10 aerosols during the 2005 dry season at a rural site in Morogoro,Tanzania

An intensive aerosol field campaign was carried out from 11 July to 11 August 2005 (dry season) at a rural site in Morogoro, Tanzania. The objectives were to determine the chemical composition of the atmospheric particulate matter (PM) and to examine to which extent the gravimetric PM mass can be explained by the measured aerosol components. Two low‐volume filter samplers were deployed, a PM₁₀ filter holder with two Whatman QM‐A quartz fibre filters in series and a Gent PM₁₀ stacked filter unit (SFU) sampler with coarse and fine Nuclepore polycarbonate filters. The samplers operated in parallel and a total of 51 parallel collections were made. All samples were analysed for the PM mass by weighing. Depending on the sampler type and/or collection substrate, further analyses were performed for 25 elements by particle‐induced x‐ray emission spectrometry, for major water‐soluble inorganic ions by ion chromatography, and for organic carbon and elemental carbon by a thermal—optical transmission technique. The PM₁₀ mass, as derived from the SFU samples, was, on an average, 46 ± 12 µg/m³. Aerosol chemical mass closure calculations were made for this PM₁₀ mass; eight aerosol components were considered and they explained 93% of the average PM₁₀ mass. Organic matter (OM) and crustal matter were the dominant aerosol components; they accounted for, on an average, 44% and 33%, respectively, of the PM₁₀ aerosol. The large contribution from OM is thought to originate mainly from the burning of biomass, especially of charcoal and agricultural residues. Copyright © 2009 John Wiley & Sons, Ltd.     

Trace element categorization of pollution sources in the equator town of Nanyuki,Kenya

An air pollution campaign was carried out in the town of Nanyuki at four different sites during July and August 1999. Nanyuki is situated on the equator on the northwestern slope of Mount Kenya at about 1930 m above sea level. The intention of the project was to characterize aerosol elemental compositions in two size fractions, associated with specific natural and anthropogenic activities. A dichotomous impactor was used for sampling and an energy‐dispersive x‐ray fluorescence spectrometer was used for the analysis. Fourteen elements (Si, S, K, Ca, Ti, Mn, Fe, Cu, Zn, Ga, Br, Rb, Sr and Pb) were analysed in all the samples. The concentration of Pb was highest at a site in the vicinity of open‐air vehicle garages. The four sites recorded high concentrations of fine S, Cl and K. Fine Zn and Br were also measured at all the sites. In the coarse size range, the concentrations of soil‐derived elements (Si, K, Ca and Fe) were dominant. The high concentration of coarse Cl was considered to be due to the contribution of sea salt and that of S to be a contribution of gas to particle conversion of SO₂. The two elements S and Cl signified the influence of long‐distance transported aerosols. The comparatively high concentrations of fine Pb and Br signified the high rate of vehicle repairs, which is a major activity close to one of the sites. Generally, soil dust‐derived particles and those from biomass burning dominated the town aerosols. Copyright © 2004 John Wiley & Sons, Ltd.     

Concentrations and sources of trace elements in particulate air pollution,Dar es Salaam,Tanzania, studied by EDXRF

Trace elements in near‐ground atmospheric aerosols were investigated in Dar es Salaam, Tanzania. Particles were collected at two sites, one urban and one rural, during two months with different meteorological conditions. The samplers, dichotomous impactors, segregate the particles into two size fractions, fine (PM_2.5, d_a < 2.5 µ m) and coarse (2.5 < d_a < 10 µ m). A sharp cyclone was used to sample finer particles (PM₁, d_a < 1 µ m). Meteorological parameters were also examined at both sites. An EDXRF spectrometer, based on three‐axial geometry, was used for quantitative elemental analysis. Concentrations of elements heavier than phosphorus were determined. Also, the content of black carbon on the filters was measured with a reflectometer. The elemental concentrations were compared with respect to season and geographical location in the city. The levels of different species in Dar es Salaam were also compared with similar data from other African and European countries. This showed low values of Pb with respect to the size of the city and no legislation on the use of leaded petrol, that often is the main source of lead. High values of Cl were also found, as would be expected in a coastal city. The coarse particles in the air, originating from soil, had a different composition in Dar es Salaam than in Gaborone, Botswana, and the concentration of black carbon was higher than in other cities. On the basis of the data collected, source assignments were made and the following sources found; sea‐spray, soil, city road dust, biomass burning, industries and traffic. Comparing the concentrations of different elements in PM_2.5 and PM₁ revealed that black carbon, Zn, Pb, K and Br are present only in the smallest particles. Copyright © 2004 John Wiley & Sons, Ltd.     

An upgraded external beam PIXE setup for multielemental analysis of atmospheric aerosol samples

The external beam particle‐induced X‐ray emission (PIXE) setup has been upgraded by introducing a new silicon drift detector with the aim of obtaining better minimum detection limits (MDLs) at the 2 × 1.7 MV Tandetron accelerator of the Beijing Normal University in China. The upgraded external beam PIXE setup is equipped with two silicon drift detectors for PIXE analysis of low and high Z elements. A surface barrier detector for Rutherford backscattering spectrometry monitors beam and helium flow. Two kinds of aerosol filter samples (quartz fiber filters and Teflon filters) were studied. A 200‐μm thick Mylar absorber in front of the medium‐high energy X‐rays detector was adopted, and it got the best MDLs for atmospheric aerosol samples analysis. Multielemental analysis of quartz fiber filter aerosol samples was achieved. For more accurate and better MDLs of low Z elements in PIXE analysis, it is necessary to keep sufficient helium flow behind the thin samples.     

Identification of aerosol particle sources in semi‐rural area of Kwabenya,near Accra,Ghana, by EDXRF techniques

Small aerosol particles have for a long time been known to be harmful to humans, and are today regarded to cause a larger number of deaths than traffic accidents globally. Energy dispersive x‐ray fluorescence (EDXRF) is a well known method that has been used for identification of toxic as well as non‐toxic elements in the particles. The combination of elements will together with other information help to identify the sources and predict the effects of particles on environment and human health. The present work was conducted in Kwabenya, a suburb of the capital Accra of Ghana, which is frequently exposed to Harmattan dust from the Sahara–Sahel region. In total 171 filters each of PM2.5 and PM(2.5–10) were collected during 1 year. Levels of elements, black carbon (BC) and mass, were determined for both particle sizes. Principal component analysis (PCA) was performed on the datasets from Harmattan and non‐Harmattan periods. The daily average of PM10 was very high, 179 µg m^?3 and the BC contents were 4 µg m^?3. The presence of crustal elements was large in PM(2.5–10) as well as in PM2.5, and had a more than tenfold increase in PM(2.5–10) during the Harmattan period. Major characteristic elements for different sources were identified from correlation coefficients and regression analysis of the data. Sahara sand aerosol was the major source in both study periods, but influence from biomass burning, sea‐spray and metal industries was also observed. Copyright © 2009 John Wiley & Sons, Ltd.     

Comprehensive microanalytical study of welding aerosols with x‐ray and Raman based methods

A comprehensive analysis of individual welding fume particles of different size fraction has been performed by applying of an innovative combination of the energy‐dispersive x‐ray fluorescence spectroscopy (EDXRF), micro‐Raman spectroscopy (MRS) and electron probe microanalysis (EPMA). Owing to this set of analytical techniques, a systematic study of the chemical composition along with the size, morphology and structure parameters of the collected welding particles was performed. The results show distinct interdependencies between the particles' elemental composition and their sizes and structures, which are consistent with commonly assumed mechanisms of their formation and evolution. In particular, interactions between the particles of fine and coarse fractions as well as regularities in distribution of the most toxic welding fume components (Mn and its oxides) have been observed. Copyright © 2007 John Wiley & Sons, Ltd.     

A tentative study of urban and suburban fine particles (PM2.5) collected in Ouagadougou,Burkina Faso

The aim of the study was to determine the mass, black carbon (BC), and elemental concentrations in fine particles (PM_2.5) and their variations at two sites in Ouagadougou, the capital city of Burkina Faso. The weather situation in Ouagadougou during the field campaign was dominated by high pressure with variable cloudiness and no precipitation. Diurnal temperatures varied between 19 and 38 °C and relative humidity between 10 and 60%. Winds in Ouagadougou were generally coming in from the north, showing a diurnal pattern with gusts of up to 6 m/s during daytime, while evenings and nights were calmer with very stable atmospheric conditions. However, during part of this field campaign, a period of nighttime moderately stable atmospheric conditions occurred with increased wind speed and more easterly winds. Cyclones were used for the PM_2.5 particle collection at both sites. The elemental analysis was done using energy dispersive x‐ray fluorescence (EDXRF) spectroscopy. Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, Br, Rb, Sr, and Pb were identified and quantified in most of the samples. The particle mass concentration was 27–164 µg/m³ while BC varied between 1.3 and 8.2 µg/m³. No influence of leaded gasoline was found. Soil dust was identified as a major component of the particles, which was confirmed by comparing with the elements in a soil sample. A significant difference in elemental, BC, and mass concentrations was seen between periods with very stable and moderately stable atmospheric conditions. Copyright © 2009 John Wiley & Sons, Ltd.     

A new microfocus x‐ray source,iMOXS, for highly sensitive XRF analysis in scanning electron microscopes

Scanning electron microscopes are usually equipped with energy‐dispersive X‐ray detectors for electron probe microanalysis. This widespread analytical method allows investigators to determine the elemental composition of specimens with a spatial resolution of about 1 µm. However, owing to the electron–specimen interaction, the emitted spectra reveal, in addition to characteristic lines, also a high level of continuous bremsstrahlung background. As a result, elements with low concentrations cannot be identified. The minimum detection limit can be diminished by two orders of magnitude if the characteristic lines are excited as fluorescence by an additional x‐ray source. In this case, the emergence of bremsstrahlung is considerably reduced. Combining a high‐brilliance microfocus x‐ray tube with efficient polycapillary optics enables one to realize an experimental arrangement for performing local fluorescence analysis at the same point where the electron beam hits the sample. The polycapillary optics under consideration focuses the emitted x‐radiation onto focal spots between 30 and 100 µm in diameter. Count rates of several thousands cps have been achieved. Elemental maps have been obtained by means of the motorized specimen stage of the microscope. Copyright © 2005 John Wiley & Sons, Ltd.     

Size‐resolved analysis of fine and ultrafine fractions of indoor particulate matter using energy dispersive X‐ray fluorescence and electron microscopy

We used a multistage PIXE inertial impactor with nine different aerodynamic diameter ranges (between 16 and 0.06 μm) to sample indoor particulate matter (PM). X‐ray fluorescence (XRF) measurements performed at cutoff diameters (CoDs) of 0.25, 0.5, 1, 2, 4, and 8 μm were used to identify elements in various size fractions. Anthropogenic sources were the dominant sources for fine and ultrafine particle sizes. The XRF results show that natural sources also contribute to the fine and ultrafine fractions of pollutants. Scanning electron microscopy and energy‐dispersive system analysis were performed on membranes having PM CoDs of 4, 2, 1, 0.5, and 0.25 μm. Elemental mappings show the membranes with PM of CoDs 0.25 and 0.5 μm having S as a dominant element, confirming the results obtained with XRF. Strong correlation among maps of S, N, and O show that ammonium sulfate is the major constituent at these size fractions. Other elements such as Si, Ca, Fe, Al, and Mg show up in smaller amounts at these size fractions but increase for membranes with larger particles. For size fractions larger than 0.5 μm, there is a good correlation between the elemental maps of these elements and oxygen, indicating that these elements exist mostly in oxide forms. The absence of clear N signals and the correlation between the Ca and S maps indicate that S in these size fractions is not due to ammonium sulfate. The presence of Mg, K, Cl, and Na at these CoDs shows that these elements are due to salts originating from sea breeze.     

Distribution of Pb and Zn in slices of human bone by synchrotron µ‐XRF

Synchrotron radiation‐induced micro x‐ray fluorescence analysis (µ‐XRF) at HASYLAB beamline L was used to determine the distribution of Pb and other trace elements in slices of human bone. Using a focused synchrotron x‐ray beam of about 15 µm in diameter it was found that Pb was mostly located at the outer border of the cortical bone in various samples. Ratios of Pb intensities of cortical and trabecular bone varied from 0.027 for hip head to 0.408 for proximal tibia. Additionally Ca, Zn and Sr distributions were simultaneously recorded. A remarkable association between Pb and Zn content could be observed. Copyright © 2004 John Wiley & Sons, Ltd.     

Depth‐selective elemental imaging of microSD card by confocal micro XRF analysis

A semiconductor device, a microSD card, was measured by using two XRF instruments. 2D elemental images were obtained using a micro‐XRF system with a spatial resolution of 10 µm. Elemental distributions of the near‐surface region of the sample were clearly shown. Titanium was observed in the resin constituting the sample. Nickel and gold were observed on a terminal and localization of the sample. Elemental distribution of copper reflected the circuit structure of the measurement area that was in the neighborhood of the sample surface. Moreover, the elemental depth distributions of the sample were measured by using a confocal micro‐XRF instrument. The confocal micro‐XRF instrument was constructed in the laboratory with fine‐focus polycapillary x‐ray optics. The depth resolution of the developed spectrometer was 13.7 µm at an energy of Au Lβ (11.4 keV). The elemental images obtained at near‐surface by confocal micro‐XRF were the same as the results obtained from 2D micro‐XRF. However, different Cu images were obtained at a depth of several tens of micrometers. This indicates that microSD cards consist of a few different Cu‐circuit structure designs. The elemental depth distributions of each circuit structure of the semiconductor device were clearly shown by confocal micro‐XRF. Copyright © 2013 John Wiley & Sons, Ltd.     

Planar waveguide‐resonator: a new device for x‐ray optics

Systematic investigations of the width dependence on the x‐ray beam propagation mechanism for a narrow extended slit formed by two plane dielectric plates are presented. It is shown that the mechanism of a multiple consecutive total reflection for Cu Kα radiation dominates in a slit width range s ≥ 3 µm. At the same time the manner of Cu Kα radiation propagation for super‐narrow slits s ≤ 0.1 µm is very different from the multiple total reflection mechanism. The x‐ray beam intensity proves to be constant for all this range of magnitude. This gives grounds to expect that the super‐narrow slit area is characterized by a specific type of mechanism of x‐ray beam propagation: waveguide‐resonance. A simple model for the waveguide‐resonance propagation mechanism based on the formation of a uniform x‐ray standing wave interference field in the total space of a narrow extended slit was developed. The design of a new x‐ray optical device, namely a planar x‐ray waveguide‐resonator, is proposed based on the waveguide‐resonance mechanism. Some properties of the composite planar x‐ray waveguide‐resonator are discussed. It is shown that under specific conditions the composite waveguide can demonstrate a partial tunneling effect of the x‐ray beam. The main applications of the new technique are discussed. Copyright © 2004 John Wiley & Sons, Ltd.     

Elemental depth profiling with a wire in microbeam X‐ray fluorescence analysis

This study proposes simple techniques involving the use of a thin wire set close to the sample surface to measure the elemental depth distribution in microbeam X‐ray fluorescence analysis. One is the X‐ray fluorescence detection in energy‐dispersive mode using a solid‐state detector in combination with the sample movement, and the other is in projection mode using an X‐ray charge‐coupled device camera. The minimum depth resolution (spatial resolution) obtained with a thin Mo wire is about 15 µm. Compared with a confocal depth‐profiling method, wire depth‐profile analysis is easy to implement, flexible, and has reasonable sensitivity. Copyright © 2011 John Wiley & Sons, Ltd.     

Improvement of spatial resolution of µ‐XRF by using a thin metal filter

An improvement of spatial resolution of µ‐XRF by using a thin metal filter was investigated. The size of the x‐ray beam focused by the polycapillary x‐ray lens depended on the energy of the characteristic x‐rays. Original spot sizes at the focal point were 48 µm for CrKα, 41 µm for NiKα, and 28 µm for MoKα, respectively. To make the x‐ray beam size small, Ti? Cu thin foil was placed between the output of the lens and the focal point as a metal filter to reduce the continuous x‐rays. Finally, the x‐ray microbeam size was improved to 30 µm by applying a filter. Clear 2D mapping images of Cr, Fe, and Ni in 300‐mesh stainless steel could be obtained by applying this filter. Copyright © 2008 John Wiley & Sons, Ltd.     

X‐ray fluorescence analysis of trace metals in environmental water using preconcentration with an iminodiacetate extraction disk

A simple and convenient x‐ray fluorescence analysis procedure for trace amounts of Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg and Pb in water was developed using preconcentration with an iminodiacetate extraction disk (IED). The IED was coated on both faces with commercially available laminate film to prevent x‐ray damage to the IED by strong x‐irradiation (4 kW; 50 kV, 80 mA) of the wavelength‐dispersive x‐ray fluorescence spectrometer. Lamination of the IED prolongs its life from 7 to about 200 min at 4 kW irradiation while negligibly decreasing the x‐ray fluorescence. Lowering the power of primary x‐rays to less than 1.5 kW compensated for the Hg evaporation. Linear calibration curves were obtained over the range 500 µg–5 mg for Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg and Pb. Detection limits corresponding to three times the standard deviation of the blank intensity were 0.1–0.4 µg for Mn, Co and Ni, 0.5–0.8 µg for Fe, Cu, Zn and Pb and 7 µg for Cd. A spike test for 10 µg of eight analytes, excluding Mn, showed good recoveries (90–100%) for city water and rainwater. Analytical results for municipal tap water and rainwater agreed well with values obtained using atomic absorption spectrometry. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of primary filter using theoretical intensity of fluorescent X‐rays and scattered X‐rays

A primary filter is often used for low‐concentration analysis by energy‐dispersive X‐ray fluorescence spectrometer. We determined the material and thickness of the primary filter and calculated the theoretical intensities of the fluorescent X‐rays and scattered X‐rays using lead in brass, for which the concentration is known. The filter materials were zirconium, nickel, titanium, aluminum, and molybdenum with a thickness between 20 and 125 µm. For verification, we calculated the lower limits of detection using theoretical intensities for several filters and compared them with values calculated using the measured intensities. For example, both values were similar for a 125 µm zirconium filter: 128.0 ppm using theoretical intensities and 147.7 ppm using measured intensities. The theoretical intensity values are obtained by measurements and calculations, but require no primary filters for the measurements. This method is extremely effective for selecting the optimal filter for multiple samples and elements. Copyright © 2010 John Wiley & Sons, Ltd.     

Improvements of the low‐energy performance of a micro‐focus x‐ray source for XRF analysis with the SEM

X‐ray Fluorescence (XRF) with a scanning electron microscope (SEM) is a valuable completion of the analytical capabilities of SEMs. Small and compact micro‐focus x‐ray sources are mounted to the microscope chamber, and the x‐ray spectra are monitored with conventional EDS systems. Up to now the x‐ray tubes used for the micro‐focus x‐ray sources are equipped with beryllium windows about 100 µm thick. The poly‐capillary x‐ray lenses have their transmission maximum at photon energies around 10 keV. It drops down in both low‐ and high‐energy ranges. Hence, L‐radiation from an Mo or Rh target will be strongly attenuated, and the excitation of fluorescence in the soft x‐ray range becomes very ineffective. A new micro‐focus x‐ray source was developed. It is characterised by a lower self‐absorption in the tube target, thin beryllium windows and an x‐ray optics having a large distance between its foci and the maximum of transmission at about 5 keV. Thus K line fluorescence of light elements becomes effectively excited by the L‐radiation from Mo or Rh tube targets. The detection limit for sodium oxide in glass was found to be below 1 mass%. Copyright © 2009 John Wiley & Sons, Ltd.