Use of INAA, PIXE and XRF in Homogeneity Testing of New IAEA Reference Air Filters

About 250 sets of polycarbonate (Nuclepore, Costar) membrane filters loaded with two urban air particulate matter (APM) obtained in Vienna and Prague were prepared by filtration of a watter suspension of the above APM materials. The homogeneity of both bulk APM materials and the loaded filters was tested by determining a number of elements by instrumental neutron activation analysis (INAA), proton induced X-ray emission (PIXE) and micro-X-ray fluorescence (-XRF). Relative standard deviations due to inhomogeneity (s _inh ) were below 3% for many elements in the bulk APM materials. In the loaded filters, the s _inh values increased significantly. Nevertheless, for up to 20 elements important in air pollution studies the s _inh values were below 15%, allowing target values with a reasonably low uncertainties (up to 20%) to be derived for the future use of the filters in proficiency testing of laboratories involved in air pollution monitoring.     

Analytical capabilities of anticoincidence INAA for biological materials

Sensitivities and limits of detection (LODs) for 39 elements were determined for cellulose filters, foods, and biological reference materials by anticoincidence instrumental neutron activation analysis. Compton background reduction improved many LODs by about a factor of 2, but increased LODs for elements whose radioisotopes decay with cascading γ-rays. As and Hg analyses were aided by reduction of Br and Se photopeak intensities, respectively. LODs of 0.03–0.8 μg/kg were achieved for 16 elements in cellulose filters. Typical biological material and food LODs were higher by factors of about 10–600.     

Direct determination of selected metals in refractory powder micro samples with exploding thin film excitation

The direct determination of metallic elements in powder micro samples is explored. Emphasis is placed on refractory materials prepared as alcoholic suspensions of their powders. Silver thin films are vacuum deposited on polypropylene strips and on polycarbonate membrane filters. Based on a parametric study, explosions conducted at 700 torr in Ar(60%)O₂(40%) using 4 kV, 180 J discharges are most satisfactory. Particle size studies suggest complete vaporization of particles smaller than ～10 μm independent of their boiling points. High circuit inductance and capacitance as well as O₂ added to the plasma support gas promote vaporization of larger particles. Particles which pass through a 5 μm mesh sieve can be analyzed with aqueous solution standards. Analytical curves and precision data are presented for Zr, V, Mo and Ni. Interparticle concomitant effects are not significant. Feasibility studies are presented for the direct analysis of airborne particles collected on metallized membrane filters.     

Waste cigarette filters: activated carbon as a novel sorbent for uranium removal

Uranium is important in the nuclear fuel cycle as both as an energy source and as radioactive waste. Herein, activated carbon (AC) prepared from waste cigarette filters by convenient carbonization and functionalization was chosen as the raw materials for radionuclides adsorption. Batch adsorption experiments showed that AC presented comparable UO₂²⁺ adsorption capacity (106 mg g^?1) and very outstanding selectivity. The adsorption process accorded with Langmuir model and the pseudo-second-order kinetics model well. This work combines the waste cigarette filters with the radioactive nuclear treatment materials, which may provide a new strategy for the future treatment of waste cigarette butts.

     

Quality assessment on airborne particulate matter of k0-INAA

The analysis of airborne particulate matter (APM) by k ₀-NAA was assessed using: (1) BCR reference material (RM) simulated air-filters, (2) synthetic air-filters prepared by spiking blank filters with standard solutions, and (3) real APM filters. k ₀-INAA is a suitable technique for the analysis of APM, delivering accurate and precise results. However, the quality assessment of APM analysis appears to be a difficult task.     

Determination of total mercury in environmental and biological samples using k0-INAA, RNAA and CVAAS/AFS techniques: Advantages and disadvantages

The accuracy and precision of the results obtained for total mercury in various environmental and biological samples and certified reference materials (CRMs) by various analytical methods, including k ₀-instrumental neutron activation analysis (k ₀-INAA), radiochemical neutron activation analysis (RNAA) and cold vapour atomic absorption (and atomic fluorescence) spectrometry (CVAAS/AFS) used in routine analysis in our laboratory, were investigated. Three natural matrix reference materials (RMs) from the International Atomic Energy Agency (IAEA), five CRMs from the Institute for Reference Materials and Measurements (IRMM), six CRMs from the National Institute of Standards and Technology (NIST) and one from the Jožef Stefan Institute (IJS) were analyzed. The results obtained show good agreement between certified or assigned values, and between the methods used, except for some data obtained by k ₀-INAA in biological samples. This can be explained by losses during irradiation in semi-open systems (irradiation in plastic ampoules) and/or spectral interferences. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and characterization of a set of IAEA reference air filters for quality control in air-pollution studies

Several sets of reference air filters were prepared as part of an IAEA evaluation of the performance of laboratories involved in air-pollution studies. Each set comprised three polycarbonate membrane filters, two of which were loaded with urban air particulate matter (APM) obtained in Vienna or Prague, and one unloaded filter. The filters were loaded by filtration of a suspension of the APM materials in water. The homogeneity both of bulk APM materials and of the loaded filters was evaluated and found suitable by determining several elements by instrumental neutron-activation analysis (INAA), proton-induced X-ray emission (PIXE), and micro-X-ray energy-dispersive fluorescence analysis (micro-EDXRF). After evaluation of the homogeneity, INAA, PIXE, EDXRF, atomic absorption spectrometry (AAS), inductively coupled plasma optical emission spectrometry (ICP-OES), and ICP mass spectrometry (ICP-MS) were used to characterize the filter materials and establish "target values" and their associated standard deviations for 15 elements. Problems encountered during the preparation of these unique, simulated air filters and the criteria for setting both the target values and standard deviations are presented.     

Activation autoradiography for a study of the selective and microheterogeneous distribution of Cu(II) in NH4Al(SO4)2·12H2O monocrystals

The possibility of the activation autoradiographic investigation of Cu(II) distribution in NH₄Al(SO₄)₂·12H₂O-monocrystals has been studied. The influence of irradiation and cooling times and the effect of application of filters made of neutron moderating materials on the sensitivity of the method is theoretically and experimentally evaluated.     

Some Aspects of Analysis of Single Fibers in Environmental and Biological Samples

Abstract

Nuclepore filters were used for sampling and evaluation of fibrous particles in ambient air, in liquids and in biological materials. The fiber counting and fiber size measurements were done by means of SEM-methods. The number of fibers and the distributions of fiber lengths and diameters were plotted. The specific identifications of asbestos, glass and other mineral fibrous particles were made by electron microprobe analysis. Certain elements proved to be approximative identification factors for different fibrous minerals in ambient air, in liquids, on material surfaces, or in biological materials.

For ambient air, asbestos, glass, and many other inorganic fibrous particles were found in the urban atmosphere as well as in the atmosphere of remote regions. Fibrous gypsum, fibrous ammonium sulfates, fibrous silicates, fibrous mica, and quartz were identified among these particles. Even in remote ambient air, relatively high concentrations of inorganic fibrous particles could be measured.     

Preparation and characterization of a set of IAEA reference air filters for quality control in air-pollution studies

Several sets of reference air filters were prepared as part of an IAEA evaluation of the performance of laboratories involved in air-pollution studies. Each set comprised three polycarbonate membrane filters, two of which were loaded with urban air particulate matter (APM) obtained in Vienna or Prague, and one unloaded filter. The filters were loaded by filtration of a suspension of the APM materials in water. The homogeneity both of bulk APM materials and of the loaded filters was evaluated and found suitable by determining several elements by instrumental neutron-activation analysis (INAA), proton-induced X-ray emission (PIXE), and micro-X-ray energy-dispersive fluorescence analysis (μ-EDXRF). After evaluation of the homogeneity, INAA, PIXE, EDXRF, atomic absorption spectrometry (AAS), inductively coupled plasma optical emission spectrometry (ICP–OES), and ICP mass spectrometry (ICP–MS) were used to characterize the filter materials and establish “target values” and their associated standard deviations for 15 elements. Problems encountered during the preparation of these unique, simulated air filters and the criteria for setting both the target values and standard deviations are presented.     

Examination of a procedure for the production of a simulated filter-based air particulate matter reference material

An approach for producing simulated air particulate matter (APM) deposited on filters has been developed and investigated as to its usefulness for yielding large batches of filters as a future reference material. The APM deposited on the filters was a material collected from an urban industrial area, and had been milled to approximate a material of PM-2.5 particle size distribution. The milled APM material was loaded onto filter substrates (Nuclepore) through the deposition of aliquots from a liquid suspension via vacuum filtration. It should be noted that these filters do not represent a typical PM-2.5 elemental composition, since the milling increased the proportion of crustal materials and the suspension in liquid decreased the sulfate content. Homogeneity between filters was tested using INAA (whole filter analysis) and ED-XRF and PIXE and was estimated to be in the 5% range (relative standard deviation). Homogeneity within the filters and among the filters was also tested using micro-XRF and found to be acceptable for the elements tested. The results of the tests carried out on the filters indicate that this approach is appropriate for large-scale production of similar filters for distribution as reference materials.     

Determination of iodine in biological materials by pseudo-cyclic epithermal INAA using anti-coincidence gamma-ray spectrometry and estimation of expanded uncertainties

Epithermal instrumental neutron activation analysis (EINAA) technique in conjunction with anti-coincidence gamma-ray spectrometry (AC) has been applied for the determination of ppm to ppb levels of iodine in biological materials containing high levels of Al, Br, Cl, K, Mn, and Na. Both conventional EINAA-AC and pseudo-cyclic EINAA-AC (PC-EINAA-AC) methods using a combination of Cd and B filters have been developed using Dalhousie University SLOWPOKE-2 reactor (DUSR) facility. The expanded uncertainties (EU), at about 95% confidence level, for iodine in biological materials by EINAA-AC varied between 6 and 10%. The advantages of the non-destructive PC-EINAA-AC method has been successfully demonstrated by analyzing the NIST Pine Needles (SRM 1575) containing a low amount of iodine in presence of high quantities of Mn and other interfering elements where an iodine content of 92.8 μg kg⁻¹ with an EU of 6.1 μg kg⁻¹ and a detection limit of 40 μg kg⁻¹ has been obtained at the end of fourth cycle.     

A comparison of direct thermal desorption with solvent extraction for gas chromatography-mass spectrometry analysis of semivolatile organic compounds in diesel particulate matter

Direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS) is a technique that is finding application in the characterisation of the semivolatile organic carbon fraction of ambient and combustion source particulate matter (PM) collected on filters. In this study, three DTD-GC-MS methods were assessed and compared to a conventional solvent extraction method for analysis of a mixture of target analytes in solution and of diesel PM collected on quartz filters. The target analytes included n-alkanes, hopanes, steranes and polycyclic aromatic hydrocarbons. This study showed that while the three DTD-GC-MS methods were generally comparable to the solvent extraction method, (1) the choice of calibration strategy and calibration materials has a significant impact on the measured accuracy of a method; (2) very large variations were seen in all methods for the more volatile compounds such as C₁₀ to C₁₃ n-alkanes and naphthalene; (3) accuracy, defined as difference from the known concentration of a liquid sample, ranged from 5% to 32%; (4) precision, defined as the relative standard deviation, ranged from 4% to 16%. The average difference of DTD-GC-MS results from the solvent extraction results for the diesel PM filters ranged from 20% to 40%. This difference was driven by the large number of target analytes present at relatively low concentrations (<25 pg/mm²) and their corresponding higher variability. Differences in performance among the compound classes were noted. Minimum detection limits for the DTD-GC-MS methods were on the order of 0.1 to 1 pg/mm² and were as good as or better than those obtained for the solvent extraction method.     

Characterization of dust material emitted during harbour activities by k<Subscript>0</Subscript>-INAA and PIXE

The growing concern about air quality in harbours is a result of the high impact of the operations on human health and environment. Harbour activities such loading, unloading and transport of dusty materials are important emission sources of Atmospheric particulate matter (APM). The assessment of these fugitive emissions is a difficult task because they depend on the materials, the type of operation and the meteorological scenarios. The main objectives of this work were (1) to evaluate if the techniques k₀-based Instrumental neutron activation analysis (k₀-INAA) and Particle induced X-ray emission (PIXE) are suitable techniques to assess fugitive emissions in harbours and (2) to estimate the impact of harbour activities on APM levels and composition. Several experimental campaigns were carried out in a Portuguese harbour, during unloading operations of fertilizer and phosphorite provided from Syria and Morocco. PM_2.5 and PM_2.5–10 were collected, in polycarbonate filters, by Gent samplers. The techniques k₀-INAA and PIXE were applied as sensitive analytical tools to perform a complete chemical characterization of the collected samples. Results showed that manipulation of these materials during harbour operations resulted in high emissions of particles, principally from the coarse fraction. These emissions were very affected by the granulometry and nature of the handled materials. Fertilizer emissions were characterized by high concentration of Ca, P, K, Cr, Br and Zn, whereas phosphorite handling contributed principally for the increase of Ca, P and Cr levels.     

A direct solid sampling electrothermal atomic absorption spectrometry method for the determination of silicon in biological materials

A solid sampling electrothermal atomic absorption spectrometry method for direct determination of trace silicon in biological materials was developed and applied to analysis of pork liver, bovine liver SRM 1577b and pure cellulose. The organic matrix was destroyed and expelled from the furnace in the pyrolysis stage involving a step-wise increasing the temperature from 160 °C to 1200 °C. The mixed Pd/Mg(NO₃)₂ modifier has proved to be the optimum one with respect to the achievement of maximum sensitivity, elimination of the effect of the remaining inorganic substances and the possibility of using calibration curves measured with aqueous standard solutions for quantification. For the maximum applicable sample amount of 6 mg, the limit of detection was found to be 30 ng g^− 1. The results were compared with those obtained by different spectrometric methods involving sample digestion, by electrothermal atomic absorption spectrometry using slurry sampling, by wavelength dispersive X-ray fluorescence spectrometry and by radiochemical neutron activation analysis. The method seems to be a promising one for analysis of biological materials containing no significant fraction of silicon in form of not naturally occurring volatile organosilicon compounds. The still incessant serious limitations and uncertainties in the determination of trace silicon in solid biological materials are discussed.     

The use of the <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-IAEA program in NIRR-1 NAA laboratory

The k ₀-IAEA program developed for implementation of the single comparator instrumental neutron activation analysis method (k ₀-INAA) has been used for elemental analysis with NIRR-1 irradiation and counting facilities. The existing experimental protocols for routine analysis based on the relative method were used to test the capability and reliability of the program for the analyses of geological and biological samples. The Synthetic Multi-element Standards (SMELS) types I, II and III recommended by the international k ₀ user community for the validation of k ₀-NAA method in NAA laboratories, furthermore, the following standard reference materials: NIST-1633b (Coal Fly Ash) and IAEA-336 (Lichen) were analyzed. Results obtained with the version 3.12 of the k ₀-IAEA program were found to be in good agreement with the data obtained with the established relative method using WINSPAN-2004 software. Detection limits for elemental analysis of geological and biological samples with NIRR-1 facilities are provided.     

Determination of metals, metalloids and non-volatile ions in airborne particulate matter by a new two-step sequential leaching procedure Part B: Validation on equivalent real samples

Due to the lack of proper standard materials for airborne particulate matter collected on filters, a validation scheme was developed, which is here described, to the aim of testing the application of leaching procedures performing both ions and elemental determinations on real samples of airborne particulate matter collected on filters. The scheme has been developed on a two-step leaching method (extraction in acetate buffer and acid dissolution of residue) previously developed by authors and consists of two series of tests to be run on n pairs of equivalent parallel samples filter-collected. The first series of tests aims to assess on real samples the equivalence between results obtained by the tested procedure with those obtained by the EMEP ions extraction and the EN 12341 standard methods, whereas the second aims to evaluate the reproducibility of analytical results of elemental determination in the leached and dissolved fractions; in the latter case data reliability is also evaluated as a function of the environment-intrinsic variability of real samples.To avoid errors due to sampling differences data from filter pairs were standardized both by gravimetric determination of loaded filters, according to the EN 12341 standard and by the rate [SO₄²⁻]_A/[SO₄²⁻]_B, where [SO₄²⁻] indicate the soluble sulphate concentration in the extract; in the latter case values improved for all elements and in both fractions. Results of equivalence with standard methods and reproducibility tests are evaluated as mean relative percentage differences (Δ%) and percentage elements recoveries (R%). The application of the validation scheme to the two-step leaching method is here discussed for non-volatile ions and for 17 elements detected on 22 pairs of low-volume collected PM₁₀ samples on Teflon filters.     

A simple non-invasive optical pyrometric method for plotting temperature—Time profiles of high temperature reactions in microwave ovens

A simple optical pyrometric method is described, based on a photocell with red and blue filters calibrated by the disappearing filament technique. The method, which is cheap, non-invasive and reproducible, is used for measurement of the rate of heating of solid materials such as coke, CuO or Fe₃O₄ in a microwave oven. All materials were heated under dinitrogen in a silica reaction vessel over 3 min in a 650 W oven. Coke (which contains graphitic phases) and magnetite heat smoothly to maximum temperatures of 1180 and 1050°C respectively. CuO heats erratically with plasma discharges from the surface, however when covered with a layer of coke the oxide heats smoothly achieving a maximum temperature of 1210°C. The observations are discussed.     

On the Interaction of Cold Atmospheric Pressure Plasma with Surfaces of Bio-molecules and Model Polymers

We review studies of surface-interaction mechanisms for a surface microdischarge (SMD) and an atmospheric pressure plasma jet (APPJ) with model polymers and biomolecules in our laboratory. We discuss the influence of plasma source type, operating parameters, and gaseous environments on surface modifications and biological deactivation. We focus on mild, remote conditions where the visible plasma plume does not contact the surface. For an APPJ fed with Ar, the interaction of the plasma plume with O₂ and/or N₂ gaseous environments leads to oxidation and surface-bound NO_x even on materials containing neither oxygen nor nitrogen. The APPJ also modifies photo-sensitive polymers. Using optical filters, these modifications were shown to result in part from irradiation with vacuum ultraviolet (VUV) photons in a spectral range corresponding to Ar excimer emission. No VUV-induced effects were seen for the SMD source operated with O₂/N₂. SMD treatments using O₂/N₂ mixtures result in surface oxidation and nitridation. A new surface-bound species, NO₃, has been measured on the polymers and biomolecules. Depending on the gas chemistry and film molecular structure, the NO₃ surface concentration can reach 10 %. Both surface NO₃ on plasma-treated films of lipopolysaccharide (LPS), an immune stimulating biomolecule found in bacteria such as E. c oli, and overall surface oxidation correlate with LPS biological deactivation as evaluated using an enzyme-linked immunosorbent assay. Ambient humidity was studied using the SMD and was found to decrease overall surface modifications including NO₃ and biodeactivation for O₂-rich conditions. Lastly, we discuss possible mechanisms and compare our results with published simulation studies.     

On-line preconcentration and determination of mercury in biological samples by flow injection vapour generation inductively coupled plasma atomic emission spectrometry

An FI-ICP-AES method for the determination of trace levels of mercury in biological samples has been described, which is based on the extraction of the mercury complex with 1,5-bis (di-2-pyridyl)methylene thiocarbonohydrazide (DPTH) on-line into isobuthyl-methyl ketone (IBMK). The organic phase (containing the complex) has been mixed on-line with SnCl₂ in N,N-dimethylformamide. Thus, mercury vapour can be generated directly from the organic phase and separated in a gas-liquid separation device. The detection limit for mercury is 4 ng/ml and the calibration curve is linear at least from 10 to 2500 ng/ml. The relative standard deviation for 10 replicate measurements is ±1% for 100 ng/ml of Hg(II). Results from the analysis of some certified biological reference materials are given.