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.     

Application of NAA to air particulate matter collected at thirteen sampling sites in eight Asian countries: A collaborative study

Air particulate matter (APM) samples (PM_2.5 and PM_10–2.5) were collected at 13 sampling points in 8 Asian countries and their chemical compositions were determined by using neutron activation analysis (NAA) with the k ₀-standardization method in addition to conventional comparative method of NAA. Analytical data showed that mass concentration and elemental composition of the APM collected are variable in terms of time and space, and are related to the characteristics of the sampling sites concerned. NAA was proved to be highly effective for the regional characterization of APM in chemical composition.     

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.     

The effect of SnCl4 on the radical polymerization of N-allyl-N-phenylmethacrylamide and N-allyl-N-phenylacrylamide

The effects of SnCl₄ on the radical polymerization of N-allyl-N-phenylmethacrylamide (APM) and N-allyl-N-phenylacrylamide (APA) were investigated. The polymerizations of APM and APA with dimethyl 2,2-azobisisobutyrate (MAIB) were carried out at 50°C in benzene at various concentrations (0-1.0 mol/L) of SnCl₄. The polymerization rates showed a maximum on varying the SnCl₄ concentration, while the molecular weights of the resulting poly(APM) and poly(APA) were decreased with increasing SnCl₄ concentration. In both systems, the degree of cyclization of polymers were decreased with the SnCl₄ concentration. From the IR results, the cyclic structure of the resulting poly(APM)s was confirmed to be five-membered, whereas poly(APA)s contained not only five-membered but also six-membered rings. The ¹H-NMR examination on the interactions of APM and APA with SnCl₄ revealed that these monomers form 1:1 and 2:1 complexes with SnCl₄ with fairly large stability constants. Copolymerizations of APM (M₁) with methyl methacrylate (MMA) and styrene (St) (M₂) were investigated at 60°C in benzene in the absence of SnCl₄. APM units were found to be incorporated exclusively as five-membered rings in the resulting copolymer. Monomer reactivity ratios were estimated to be r₁ = 0.29, r₂ = 4.88 for APM/MMA and r₁ = 0.66, r₂ = 5.39 for APM/St. The presence of equimolar (to APM) SnCl₄ was found to enhance the reactivity of APM toward poly(MMA) radical; r₁ = 0.24, r₂ = 2.56. © 1996 John Wiley & Sons, Inc.     

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.     

k0 and Comparator NAA: Influences and Interactions

A discussion is held on mutual influences and interactions between k ₀- and (relative) comparator-type NAA. Examples are given concerning: (1) the application of comparator-type NAA in the quality control/quality assurance of the IRMM-530 Al-0.1%Au neutron flux monitor developed for use in k ₀-NAA, (2) the utilization of the k ₀-method of calibration as a tool for the quality assurance of comparator-type NAA, (3) the introduction of corrections for detection efficiency and true-coincidence (of primordial importance in k ₀-NAA) in comparator-type NAA, (4) the development of k ₀-type standardization for use in prompt gamma neutron activation analysis, and (5) the renewal of insights in the traceability of k ₀- and comparator-type NAA.     

Measurement and evaluation of k0 factors for PGA at JAERI

In order to determine multiple elements by k ₀ standardization-based neutron induced prompt gamma-ray analysis (PGA), measurements and evaluation of k ₀ factors for the elements have been performed. The k ₀ factors using Cl as a comparator for 27 elements, which are effective for the analysis by PGA, were measured with precision almost less than 3% using the cold and thermal guided neutron beams at JRR-3M. The accuracy of the k ₀ factors were better than 10% except for the non-1/v elements of Cd and Sm. Neutron spectrum correction is necessary for common use of k ₀ factors of the non-1/v elements.     

Prompt-gamma activation analysis using thek 0 approach

Applying thek ₀ standardization method to prompt-gamma activation analysis (PGAA) offers similar benefits as in instrumental neutron activation analysis. It has been demonstrated that under constant flux conditionsk ₀-factors obtained by normalizing to a titanium comparator, measured separately, yield consistent analytical sensitivity ratios. The ratio method has been generalized by using stoichiometric compounds for the determination ofk ₀-factors. Since chlorine forms compounds with essentially everyelement and it also serves as a detector efficiency standard,k ₀ values have been determined relative to chlorine as an internal standard for several analytically important elements in two reactor facilities: the thermal guided beam at the BRR in Budapest and the cold-neutron beams at the NBSR at NIST.     

Development and applications of <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript> based NAA and prompt gamma-ray NAA methods at BARC

A summary of k ₀-based R&D work on neutron activation analysis (NAA), internal mono standard NAA (IM-NAA) and prompt gamma-ray NAA (PGNAA) is presented. The k ₀-based NAA was standardized by characterizing irradiation sites of research reactors, validated using reference materials and applied to samples of different origin. Recently IM-NAA method was developed, validated for small and large size samples and applied for the analysis of large size as well as non-standard geometry samples. Studies on PGNAA included characterization of neutron beam, determinations of detection efficiency and prompt k ₀-factors, and analytical applications.     

The application and development of k0-standardization method of neutron activation analysis at Dalat research reactor

In recent years the k ₀-NAA method has been applied and developed at the 500 kW Dalat research reactor, which includes (1) the establishment of a PC database of k ₀-NAA-related nuclear parameters, e.g., radionuclide produced, half-lives, k ₀-factors, Q ₀, _r, E _g, etc; the access to the database is able by a k ₀-NAA software or by manual; (2) the detection efficiency calibration of gamma spectrometers used in k ₀-NAA, (3) the determination of reactor neutron spectrum parameters such as a and f factors and neutron fluxes in the irradiation channels, and (4) the validation of the developed k ₀-NAA procedure by analysing some SRMs, namely Coal Fly Ash (NIST-1633b), Bovine Liver (NIST-1577b) and IAEA-Soil7. The analytical results showed the deviations between experimental and certified values were mostly less than 15% with most Z-scores lower than 2. The k ₀-NAA procedure established at the Dalat research reactor has been regarded as a reliable standardization method of NAA and as available for practical applications, in particularly for airborne particulate and crude oil samples.     

Neutron activation analysis for identification of African mineral dust transport

A Gent stacked filter unit sampler was used to collect air particulate matter (APM) in separate coarse (PM_2.5–10) and fine (PM_2.5) size fractions, at a sub-urban site in Lisbon, Portugal. The sampling was done during the year 2001 and two daily samples were taken per week. The filters were analyzed for particulate mass by instrumental neutron activation analysis (INAA). The chemical analysis of APM levels and the study of the atmospheric dynamics by back-trajectories showed that most of the PM_2.5 and PM_2.5–10 peaks events were associated with air masses transport from the Saharan desert. High mineral load in ambient particulate matter levels were registered during the Saharan dust outbreaks. The accuracy of INAA to measure Fe, Sc and Sm was evaluated by NIST filter standards, revealing results with an agreement of ± 10%. This method constituted an important tool to identify these events.     

k0 Standardization Approach in Neutron-Induced Prompt Gamma-Ray Analysis at JAERI

The k ₀ standardization method has been studied and applied at JAERI for the accurate determination of multielements by neutron-induced prompt gamma-ray analysis (PGA). The k ₀ factors for 26 elements using Cl as a comparator were measured by the cold and thermal neutron guided beams of JRR-3M with an uncertainty less than 3% except for a few elements. The k ₀ factors for most elements obtained with both cold and thermal neutrons agreed within 3%, and agreed also with those measured at other cold and thermal neutron guided beams within 10%, except for a few elements. Multielement determinations in reference materials were performed using the k ₀ factors obtained to evaluate the accuracy and precision of this work.     

Determination of major and trace elements in iron reference materials using k0-NAA

Major and trace element contents in iron ore reference materials were investigated using k ₀-instrumental neutron activation analysis (k ₀-INAA). To avoid iron interferences, radiochemical separation was developed (k ₀-RNAA). The determination of the investigated elements in the inorganic phase from hydrochloric acid solution was performed after radiochemical separation of iron by diisopropyl ether. It was found that after the Fe elimination, the limit of detection for some elements was much lower that enables their direct determination. The distribution of 39 elements (with intermediate/medium and long half-life radionuclides) after Fe removal was investigated.     

Determination of 237Np by k0 RNAA

The determination of very low concentrations of ²³⁷Np is of key-interest for environmental monitoring. The application of the k ₀-method to neutron activation analysis was not possible so far, since the k ₀-parameters were lacking. The parameters required for the k ₀-method are: the effective resonance energy r, the resonance integral (1/E) to 2200 m^.s^-1 cross section ratio Q ₀, and the k ₀ values. In this work, the experimental values of these parameters were determined by using two nuclear reactors with very different flux characteristics.     

Monitoring of environmental contaminants: 10 years of application of k0-I INAA

Examples of the application of k ₀ standardized instrumental neutron activation analysis (k ₀ -INAA) to aerosols and biological monitors in the last 10 years at Instituto Tecnológico e Nuclear (ITN) are given. As an analytical technique, INAA, in association with the k ₀ method was applied to these materials in four different projects, aiming at monitoring concentrations of heavy metals and others elements in the atmosphere in the Portuguese territory. In these studies we analysed the lichen Parmelia sulcata Taylor and olive tree bark as monitors as well as aerosol samples. For each project some representative results are presented, followed by a discussion of the application of this technique to environmental studies.     

The recommended k0-factors for neutron-induced prompt gamma-ray analysis and the prompt gamma-ray emission probabilities

Recommended k ₀-factors for gamma-lines of 24 elements useful for neutron-induced prompt gamma-ray analysis (PGA) and which are not influenced by neutron spectrum differences were obtained from the k ₀-factors measured with the cold and thermal neutron guided beams of JRR-3M, by statistical calculation. The prompt gamma-ray emission probabilities were derived from the recommended k ₀-factors using atomic weight, isotopic abundance and thermal neutron capture cross section all related to the k ₀-factors, for which one can obtain accurate data. The derived gamma-ray emission probabilities for the light elements (H to Ca) agreed well within ±10% with those of the ENSDF values, which reflect recent data while the agreement for heavy elements (Ti to Pb) was ±40% with those of the ENSDF, which are still composed of old data. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chemical profile of fugitive particulate emissions

Fugitive emissions pose problems both for general air quality management as well as for the operational management of the facilities. In harbours, activities such loading, unloading and transport of dusty materials are important sources of particulate fugitive emissions. Therefore, there is a growing concern about air quality in these areas as a result of the high impact of the operations on human health and environment. The objectives of this study were to estimate the impact of harbour activities on air particulate matter (APM) levels and to compile an inventory of chemical profiles of harbour particulate fugitive emissions. This preliminary work was based on experimental campaigns carried out in a Portuguese harbour when different types of bulk materials were handled. High time resolution monitors were installed close to the unloaded area and recorded APM concentrations and meteorological variables. PM_2.5 and PM_2.5–10 were collected during unloading operations and a complete chemical characterization of collected samples was made by the techniques k ₀-instrumental neutron activation analysis and particle induced X-ray emission. Results showed that manipulation of materials during harbour operations resulted in high emissions of particles, especially from the coarse fraction. These emissions were very affected by the granulometry and chemical composition of the handled materials and by the meteorological conditions.     

Interacalation of pyridine and its derivatives into crystalline bismuth molybdenum hydrous oxide

The use of thek ₀-standardization method in instrumental neutron activation analysis gives good accuracy and precision. The analysis time can be reduced drastically by employing software for thek ₀-standardization calculations. In this work samples were irradiated in a TRIGA reactor and the gamma spectrum was analysed by Sampo 90 and thek ₀-standardization by the KAYZERO/SOLCOI code (DSM Research). The efficiency measurement and the peak to total ratio at the reference and other geometries were measured and tested for their accuracy by analysing some reference materials. Reference materials such as SRM 1572 (Citrus leaves), SRM 1573 (Tomato leaves), SRM 1575 (Pine needles), IAEA Soil-7 (Soil) and SRM 1646 (Estuarine sediment) were analysed for the major, minor and trace element contents. The results were in good agreement with the certified or literature values. The recently released IAEA 140 (Sea plant homogenates) was also analysed for 28 elements.     

Determination of water-soluble and insoluble compounds in size classified airborne particulate matter

The elemental composition of water soluble and acid soluble size-fractionated airborne particulate matter (APM) was investigated. PM2.5 and PM2.5-10 samples were collected every three days from October 2006 to October 2007 in Buenos Aires, Argentina. The collection was performed on Nucleopore® filters using a GENT sampler. Samples containing fine and coarse particles were subjected to an aqueous leaching to obtain information on the dissolution behaviors of ions, metal and metalloids. Key elements namely, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Se, Ti and Zn were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). In the aqueous fractions, Cl⁻, SO₄²⁻, Na⁺ and NH₄⁺ were determined by high performance liquid chromatography (HPLC). A (6:2:5) mixture of nitric, hydrochloric and perchloric acids was used for leaching metals from the residual filters. For validation of the extraction procedure, the ICP OES measurements the Standard Reference Material NIST 1648 (Urban particulate matter) was subjected to the same analytical procedure that the samples loaded with APM. Total analyte concentration varied from 333.2 μg g^− 1 (equivalent to 3.7 ng m^− 3) for Ti to 692 mg g^− 1 (equivalent to 2.47 μg m^− 3) for Ca.     

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.