Determination of Silicon in Airborne Particulate Matter By XRF and LA-ICP-MS

This study directly analyzes Si in airborne particulate matter by laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) as well as X-ray fluorescence (XRF).     

Elemental determination of airborne particulate matter by XRF

Multielement determination of airbone particulates collected on PTFE-membrane filters by XRF, and possibility of using this technique in Receptor Model analysis were investigated. In order to keep the background interference as low as possible, special emphasis was therefore laid on the setup of optimized analytical procedures for XRF measurement. An intercomparison between INAA and XRF methods was performed by analyzing the same filter samples.     

A comparison of laser ablation inductively coupled plasma mass spectrometry,micro X-ray fluorescence spectroscopy,and laser induced breakdown spectroscopy for the discrimination of automotive glass

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), micro X-ray fluorescence spectroscopy (μXRF), and laser induced breakdown spectroscopy (LIBS) are compared in terms of discrimination power for a glass sample set consisting of 41 fragments. Excellent discrimination results (> 99% discrimination) were obtained for each of the methods. In addition, all three analytical methods produced very similar discrimination results in terms of the number of pairs found to be indistinguishable. The small number of indistinguishable pairs that were identified all originated from the same vehicle. The results also show a strong correlation between the data generated from the use of µXRF and LA-ICP-MS, when comparing µXRF strontium intensities to LA-ICP-MS strontium concentrations. A 266 nm laser was utilized for all LIBS analyses, which provided excellent precision (< 10% RSD for all elements and < 10% RSD for all ratios, N = 5). The paper also presents a thorough data analysis review for forensic glass examinations by LIBS and suggests several element ratios that provide accurate discrimination results related to the LIBS system used for this study. Different combinations of 10 ratios were used for discrimination, all of which assisted with eliminating Type I errors (false exclusions) and reducing Type II errors (false inclusions). The results demonstrate that the LIBS experimental setup described, when combined with a comprehensive data analysis protocol, provides comparable discrimination when compared to LA-ICP-MS and μXRF for the application of forensic glass examinations. Given the many advantages that LIBS offers, most notably reduced complexity and reduced cost of the instrumentation, LIBS is a viable alternative to LA-ICP-MS and μXRF for use in the forensic laboratory.     

Investigation of different types of filters for atmospheric trace elements analysis by three analytical techniques

Different atmospheric aerosol samples were collected on three types of filters. Disks of both loaded and clean areas of each kind of filter were investigated by XRF, PIXE and Scanning Electron Microscope (SEM) methods. The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of fiters are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These have much lower blank element concentration values than the glass fibres and ash free filters. It was found also that the PIXE method is a more reliable analytical technique for atmospheric aerosol particles than the other methods.     

Comparison of ED-XRF and LA-ICP-MS with the European reference method of acid digestion-ICP-MS for the measurement of metals in ambient particulate matter

A comparison study of the measurement of metals in ambient particulate matter collected on air filters, using energy-dispersive X-ray fluorescence (ED-XRF), laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and wet chemical digestion followed by ICP-MS analysis according to the European ‘reference method’ EN14902, is presented. Whilst it is shown that the methods have a low systematic bias with respect to each other, overall they do show a high random variability, and when considered individually using regression methods, some analytes have shown bias with respect to the EN14902 method. The low systematic bias observed is not unexpected since both the ED-XRF and LA-ICP-MS methods have been calibrated using results from the EN14902 technique. The uncertainty of each analysis has been estimated and compared with the data quality objectives for uncertainty specified in the relevant European air quality legislation. This has tentatively shown that approximately 75% of the analyses using ED-XRF and LA-ICP-MS meet the requirements of the legislation. However, improvements in repeatability and calibration methods for both ED-XRF and LA-ICP-MS would be needed before these methods were truly applicable for routine use in air quality measurements of this type.     

Comparison of different types of filters for atmospheric trace element analysis by three analytical methods

Different atmospheric aerosol samples were collected on three types of filters. From both of the loaded and clean areas of each kind of filter, different disks were cut and investigated by XRF, PIXE and scanning electron microscopy (SEM). The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of filter are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These filters have much lower blank element concentrations than the glass fiber and ash free filters. It was found also that PIXE is a more reliable analytical technique for atmospheric aerosol particles than the other methods used.     

Multi-element analysis of airborne particulate matter by various spectrometric methods after microwave digestion

A microwave digestion procedure in combination of the measurement of various spectrometric methods including atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry was developed for the multi-element analysis of airborne particulate matter collected on PTFE filters by a dichotomous sampler. In order to achieve more sensitive and rapid multi-element analyses, special PTFE-lined digestion vessels were used. It was found that complete digestion of airborne particulates with an acid mixture of HNO₃-HClO₄-HF (3:7:1, v/v) can be achieved in the microwave-irradiated closed vessel system and direct spectroscopic measurement of the digested sample after appropriate dilution. A recovery study was conducted using a multi-element standard and NIST Standard Reference Material 1648 Urban Particulate. Sixteen major, minor, and trace elements in airborne particulate matter were determined.     

Comparative studies on metal determination in airborne particulates by LA-ICP-MS and furnace atomization non-thermal excitation spectrometry

Air pollution, especially by metallic aerosols, has toxic effects on soil and water, biological environment, and human health. Therefore the determination of metal contents in airborne dust is of particular relevance. For measurements with high resolution in time and space a rapid analytical method is necessary as well as short and efficient sampling. Two techniques for rapid multielement trace analysis were compared with respect to the determination of metallic, aerosol concentration in air. In both methods air was sucked through a filter material which subsequently was analyzed without any additional pretreatment. When La-ICP-MS was applied, quartz fibre filters were used as collectors which were then ablated employing a Nd:YAG laser for analyses by ICP-MS. With FANES a special porous graphite tube acted as an efficient particle collector. When inserted into the FANES source the graphite tube simultaneously serves as thermal atomizer and hollow cathode so that collected particulates were vaporized and excited in the tube for optical emission spectrometry. For signal registration an echelle polychromator was used. With FANES detection limits based on the 3 -criterion range between 0.2 and 2 ng/m³ for 10 elements. With quartz filters comparable results can be obtained only after enrichment by more than a 500-fold air volume. Measured metallic aerosol concentrations in ambient air by both methods do not differ within the 95% significance level.     

Atomic emission spectrometric analysis of airborne particulate matter by direct nebulization of suspensions into the inductively-coupled plasma

A method is described for the rapid, direct emission spectrometric determination of iron in airborne particulate matter collected on polystyrene fiber filters using a conventional high-volume sampler and a Japanese low-volume sampler. The suspension prepared by dissolving the filter material in xylene was directly nebulized into the inductivelycoupled plasma excitation source. An ultrasonic immersion device was used for stirring purposes. Particles within the size range 0.1–100 μm in diameter are collected on the high-volume filters, while the largest particles on low-volume filters do not exceed 10 μm in diameter. The difference in the particle size composition entailed the use of a separate set of standard suspensions for each sample type. Standard suspensions for calibration were prepared from NBS SRM-1648 (urban particulates) as originally received and from its ground powder for high-volume and low-volume samples, respectively. The relative standard deviation was usually below 5%, which is acceptable for large-scale air pollution survey work. The possibility of determining other major and minor elements in airborne particulate matter was also examined.     

Fast determination of trace elements on aerosol-loaded filters by X-ray fluorescence analysis considering the inhomogeneous elemental distribution

X-ray fluorescence (XRF) analysis was successfully applied for the determination of Ca, Cu, Fe, Mn, Ni, Pb, V and Zn on aerosol filters with a diameter of 150 mm. Ambient aerosol was collected on quartz-fibre filters by Digitel high-volume samplers. For XRF analysis three small filter pieces with a diameter of 32 mm were cut out of each filter, considering the radial dependence of elemental distribution on the filter. Elemental concentration decreases by 8–10% from the centre to the outer circle for coarse mode elements. Distribution of fine mode elements display only small radial dependence (2–4%). Results of quantitative analysis by XRF were compared with atomic spectrometric methods (GF-AAS, ICP-OES). The good agreement between the methods confirmed the application of XRF spectrometry for routine analysis of filter samples loaded with ambient aerosol.     

Fast determination of trace elements on aerosol-loaded filters by X-ray fluorescence analysis considering the inhomogeneous elemental distribution

X-ray fluorescence (XRF) analysis was successfully applied for the determination of Ca, Cu, Fe, Mn, Ni, Pb, V and Zn on aerosol filters with a diameter of 150 mm. Ambient aerosol was collected on quartz-fibre filters by Digitel high-volume samplers. For XRF analysis three small filter pieces with a diameter of 32 mm were cut out of each filter, considering the radial dependence of elemental distribution on the filter. Elemental concentration decreases by 8-10% from the centre to the outer circle for coarse mode elements. Distribution of fine mode elements display only small radial dependence (2-4%). Results of quantitative analysis by XRF were compared with atomic spectrometric methods (GF-AAS, ICP-OES). The good agreement between the methods confirmed the application of XRF spectrometry for routine analysis of filter samples loaded with ambient aerosol.     

Determination of leachable uranium in airborne particulates

The uranium content of airborne particulates collected on cellulose filters was investigated. As a case study, filter samples from the large area of Thessaloniki, Greece, were used. For the uranium determination instrumental neutron activation analysis was used. To obtain equal counting conditions for all samples after irradiation, independent from the initial matrix, uranium was leached from the filter by using a 0.1M NH₄HCO₃ solution, forming a stable uranyl complex [UO₂(CO₃)₃]. This complex was absorbed in a batch process on a small amount of chelating ion exchanger Srafion NMRR, which was directly irradiated in the reactor of the NCSR Demokritos. The study showed that over the investigated time period in 1997 the mean concentration was found to be 0.047 ng U/m³. In relation to the collected amount of airborne particulates having a mean concentration of 0.52 ng/gU. It can be assumed as a natural uranium level in the environment.     

The determination of ammonium ion in airborne particulates with selective electrodes

The accurate and rapid measurement of ammonium ion in airborne particulates is described, with particular reference to so-called high-volume air samples collected on glass-fibre filters. The method involves aqueous extraction of a part of the filter followed by analysis with a selective electrode; an Orion ammonia electrode and a Beckman ammonium electrode were compared. Varying ionic strength of the sample extracts had no effect and small interferences by other elements with the Beckman electrode could be taken into account. For a typical air sample of 2000 m³, the ammonium content could be determined accurately down to 0.03 μg m^-3. The accuracy was established by comparison with an absorptiometric method. Recovery of standard added ammonium was quantitative. Three different methods of extraction were compared.     

Unsicherheiten bei der Abscheidung von Schwebstaub an Filtern

Summary Different samples of airborne particulate matter collected successively by highly effective aspirators were analysed for Al, Si, S, K, Ca and Fe by XRF. The results show that there is not only a distinct alteration of the content during short intervals of time, but also a remarkable change in the quantitation of the particular elements in the dust composition. By synchronous aspiration in a distance of 1 m it was possible to show that the local distribution is also different. In the experiments to be reported there are differences greater then 10% in respect of particular elements. In comparison with this, the decomposition of the dust during the aspiration is not significant. But it has to be taken into consideration if only parts of the filter disk are used for analysis.     

Extraction of arsenic species from airborne particulate filters—Application to an industrial area of Greece

In the present study, the extraction of the arsenic species arsenite (As(III)), arsenate (As(V)), monomethyarsonic (MMA) and dimethylarsinic acid (DMA) from airborne particulate filters was investigated and optimized. For this purpose, total suspended particulate matter as well as size fractionated aerosol samples were collected from the industrial area of Aspropyrgos, Greece, in glass fibre and polycarbonated filters, respectively. Among H₃PO₄ and HCl, tested in various concentrations, concentrated HCl was found to be the most effective extractant for arsenic from both polycarbonated and glass fibre filters, without provoking any arsenic species transformation. However, the quantitative extraction of arsenic species from glass fibre filters required the subsequent washing of the filters with ultrapure water after their leaching with concentrated HCl. The developed procedure was applied to airborne particulate filters for arsenic speciation in Aspropyrgos' atmosphere. The results showed an enrichment of As in the fine (PM_2.5) compared with the coarse (PM_10–2.5) fraction of airborne particulates, while As(V) was found to be the predominant arsenic species in all samples. Finally, As concentration in the PM₁₀ fraction, for the investigated area and time period from December 2004 to June 2006, was below the target value of 6 ng As m^− 3, referred in the Directive 2004/107 of European Union.     

Determination of dithiocarbamate pesticides in occupational hygiene sampling devices using the isooctane method and comparison with an automatic thermal desorption (ATD) method

Two new methods for the determination of dithiocarbamate pesticides in occupational hygiene sampling devices are described. Dithiocarbamate spiked occupational hygiene sampling devices, consisting of glass fibre (GF/A) filters, cotton pads, cotton gloves and disposable overalls, were reduced under acidic conditions and the CS2 evolved as a decomposition product was extracted into isooctane. The isooctane was then analysed using gas chromatography with mass spectrometry, for CS2, which provided a quantitative result for dithiocarbamates. Recoveries obtained were generally within a 70-110% range and reproducibilities better than 15% RSD were typically achieved. The method has been successfully applied to samples collected during occupational exposure surveys. A second method employing automatic thermal desorption-gas chromatography-mass spectrometry (ATD-GC-MS) has also been developed and applied to the direct analysis of GF/A (airborne) samples. The method relies on the thermal degradation of dithiocarbamates to release CS2, which is used to quantify the analytes. Thiram spiked GF/A filters gave an average recovery of 107% with an RSD of 4%. The performance of the two analytical methods were directly compared by analysing sub-portions of GF/A filters collected during a survey to evaluate occupational exposures to thiram during seed treatment operations. Both methods performed well for the analysis of airborne (GF/A) samples and produced results in good agreement. ATD-GC-MS is the preferred method for studies involving GF/A (airborne) samples only. Because of the wider applicability of the isooctane method for other sampling devices, it is the preferred choice when carrying out surveys which require a dermal as well as respirable exposure assessment.     

Assessment of X-ray photoelectron spectroscopy for analysis of particulate pollutants in urban air

XPS was used to determine hourly and seasonal changes in urban airborne airborne particulates collected in London, UK. Particles were collected on a Burkard spore trap and on PTFE filters for hourly and daily readings, respectively, at periods during the summer and winter. Analysis within 24 h of collection was advisable to avoid build-up of surface contamination from the atmosphere. Carbon and oxygen species dominated the particulate surface with traces of Na+, Mg2+, Ca2+, SiO2, Cl-, NH4+, NO3- and SO4(2-) present. Major species could not be identified on particles collected by the Burkard spore trap as the peaks from the particles coincided with peaks from the tape in the O 1s and C 1s regions. In addition, particle loads were insufficient to establish changes in surface chemistry of the remaining trace species on an hourly basis. Carbon species could be identified for particles collected on PTFE filters as the binding energies for particles and PTFE are separated by 8 eV in the C 1s region. Three regions were identified, namely C-H/C-C, C-O/C-N and C=O/COO-. There was evidence of higher levels of soot during the winter due to more anthropogenic activity, which is in agreement with other data. Fe was a major element detected by electron probe microanalysis in the bulk of winter particles but not on the surface, implying an organic coating on the particles sufficiently thick (> 2 nm) to absorb the Fe photoelectrons.     

Study of quality control and metal distribution in urban airborne particulates

In this investigation, results of 33 elements in airborne samples collected continuously over nine urban locations are discussed. Inductively coupled plasma-atomic emission spectrometry technique was used for determining concentration of metals. Quality control was established prior to analysis of real air samples. The guidelines followed are based on USEPA Compendium Method IO-3.4. Uncertainty in analysis was also established. Based on the concentration of metals in airborne particulates, we attempted to study the metal distribution characteristics in ambient air at various urban locations. Metals such as Al, Ca, Fe were comparatively at higher concentrations than the other elements under study at most of the locations. The city vehicles operate on lead-free fuels; however, concentration of lead in urban dust was observed in the concentration range of 0.33–6.24 μg/m³. Soil samples were also collected from sites close to the air sampling locations. Soil samples were also analysed for metal content. Enrichment factor was determined for elements measured at nine urban locations. The data supports interpretation of results in terms of contribution of metals in airborne particulates from anthropogenic and noncrustal origin.     

Elemental Analyses Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) of Geological Samples Fused with Li2B4O7 and Calibrated Without Matrix-Matched Standards

 Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used as a complementary technique to X-ray fluorescence (XRF), for multi-element analysis of geological samples fused with lithium-tetraborate Li₂B₄O₇). Different calibration strategies using external non-matrix matched reference materials were investigated. Various internal standards were tested, including the use of Li from the flux, and the use of the naturally occurring internal standards, Si or Ca. The use of a naturally occurring standard is not as efficient as this required a prior analysis of the samples using XRF. The obtained values for the analysis of geological reference materials were compared with consensus literature values, and satisfactory agreement was found. Laser pits, which were formed, had a diameter of 80 μm and 3–5 replicates on each fused disc were measured. The reproducibility of the method was better than 10% for concentrations above 1 μg/g and better than 15% for lower concentrations. The use of Li as the internal standard offers the possibility of multi-element determinations in geological samples, which have an unknown composition when the laser ablation analysis is carried out. However, using the calculated stoichiometric composition of the lithium-tetraborate for the calculation of the Li concentration leads to a constant deviation from the recommended values. Therefore, it was necessary to determine the Li concentration within each sample batch using at least one lithium tetraborate fused geological reference material. This resulting Li concentration in the beads was then used for all subsequent samples in a run. Limits of detection, reproducibility, deviation from reference values indicate the potential of LA-ICP-MS for such bulk analysis without matrix matched calibration standards.     

基于激光剥蚀-电感耦合等离子体质谱技术的生物元素成像分析

生物体内的微量元素具有十分重要的生物功能,也与许多疾病密切相关。现代生物医学的研究亟需能在组织、细胞等不同水平上原位分析生物样品中微量元素的分析方法。本研究建立了激光剥蚀-电感耦合等离子体质谱( LA-ICP-MS)原位分析生物样品的方法。采用线扫描模式和较小的激光输出能量(﹤1 J/cm2),得到了鼠脑切片和金纳米颗粒暴露后单细胞的金属元素成像图。 LA-ICP-MS具有空间分辨率高、检出限好、运行成本较低等优势,有望在生物医学研究中得到更广泛的应用,发挥更重要的作用。