Characterization of sampling behavior for multielements in NIST SRM 2703

Sampling behavior of multielements for NIST SRM 2703, a marine sediment, was studied with sample sizes from 1 mg down to ng level by a combination of INAA, PIXE and SRXRF. On 1 mg sample size level, sampling behavior for multielements in NIST SRM 2703 and its parent SRM 2702 were comparatively characterized by using INAA combining with Ingamells model. Results showed that sampling uncertainties for 12 elements of both materials were found to be better than 1%, and those of four other elements in SRM 2703 better than in SRM 2702. At sample sizes not able to be accurately weighed (<1 mg), PIXE and SRXRF were used and the effective sample sizes estimated. Sampling uncertainties for nine elements were found to be better than 1% at sample sizes of tenth mg level, and those for six elements better than 10% on ng levels.     

Role of NAA in the characterization of sampling behaviors of multiple elements in CRMs

Taking the advantage of the high precision and accuracy of neutron activation analysis (NAA), sampling constants have been determined for multielements in several international and Chinese reference materials. The suggested technique may be used for finding elements in existing CRMs qualified for quality control (QC) of small size samples (several mg or less), and characterizing sampling behaviors of multielements in new CRMs specifically made for QC of microanalysis.     

Nuclear analytical methods in quality control of microanalysis

Quantitative calibration and quality control have been a major bottleneck in microanalysis due to the lack of natural-matrix CRMs certified at sample sizes compatible with those of unknown samples. In this paper, a solution is described to characterize sampling behavior for individual elements, so as to identify elements homogeneous enough at stated sample size levels in given CRMs/RMs. By using a combination of several nuclear analytical techniques, INAA-EDXRF-μPIXE, sampling behavior for individual elements can be characterized at sample size levels from grams down to pg. Natural-matrix CRMs specifically for QC of microanalysis may thus be created. Additional information in certificates of these new generation CRMs is imagined. This revised version was published online in July 2006 with corrections to the Cover Date.     

57Fe Mössbauer, XRD and DTA Study of the Crystallization Behavior of Calcium Aluminate Glass Containing Iron(III)

Certifications of trace elements in existing CRMs, especially biological CRMs, are far from satisfactory. Neutron activation analysis (NAA) for its inherent advantages combined with newly established parametric standardization, may contribute to improve this situation. The continuing progress of the hybrid extended k ₀-relative NAA technique developed in our laboratory is discussed. Examples are given to show the reliability of the method in certification of multielements. RNAA is still one of the best methods, or even the method of choice, in analysis at sub-g/g concentration levels. The suitability of the technique for this purpose has been studied through the determination of rare earth elements at ng/g concentration level in two Chinese biological CRMs using both RNAA and ICPMS. Sampling behaviors of multielements in CRMs have been studied by INAA in an effort to develop CRMs suitable for analysis with small sample sizes.     

Combined application of INAA and PIXE for studying the regional aerosol composition in Southern Africa

As part of the SAFARI-92 biomass buming experiment, aerosol collections were carried out with several size-fractionating sampling devices at a number of sites in Southern Africa. One of the samplers used at all ground-based sites was a stacked filter unit (SFU). The SFU samples were analyzed by both INAA and PIXE analysis. The present paper gives an intercomparison of the analytical results obtained in order to assess the accuracy and to check the quality assurance of the analytical procedures. Twenty-one common elements were determined by both INAA and PIXE. Concentrations of 13 elements (i.e., Na, Mg, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Br) were generally measured with sufficient precision in both techniques for performing the intercomparison. The INAA and PIXE data were compared in terms of PIXE/INAA concentration ratios on a sample by sample basis for the coarse and fine size fraction separately. the atmospheric concentrations for K, Mn and Fe agreed within 5–10%, the agreement between the data for the other common elements was typically better than 15%. Possible explanations for lower than 1.0 ratios for Cl, Br and Na are presented. The common elements were classified into groups according to their detectability and sensitivity in each technique.     

Metrological role of neutron activation analysis. III. Role of INAA in sampling behavior characterization

The minimum sample size, usually 100 mg or larger, is often the only information given on certificates of existing certified reference materials (CRMs) to describe sampling behavior. This value is not only too large for quality control requirements of microanalysis, but also too general to reflect the strong element-specific nature of the sampling behavior of solid materials. In this paper, the third and final of the series, we explain the need for CRMs with sampling behavior characterized for individual elements and describe the unique role of instrumental neutron activation analysis in sampling behaviour characterization. Received: 19 March 2001 Accepted: 2 October 2001     

Low uncertainty determination of manganese and vanadium in environmental and biological reference materials by instrumental neutron activation analysis

The elements Mn and V were determined by INAA in about 5 mg and 100 mg aliquots of NIST SRM 1648 to elucidate discrepancies between our previous results for the 0.5 mg to 15 mg aliquots and the NIST certified and/or information values. Simultaneously, other NIST SRMs 1633a, 2704, and BCR CRMs 038, 101 and 143 were also analyzed. Special attention was given to evaluating and minimizing uncertainties of all steps of analysis. Our results compared very well with the respective certified and/or information values (if available) of all SRMs and CRMs studied, except for NIST SRM 1648. For this SRM we have found significantly lower results than the NIST values which suggests that the NIST values are positively biased by about 10%. A new value for V in BCR CRM 143 was also obtained.     

Assessing sample representativeness for inorganic chemical investigation of invertebrates by INAA

The quality of environmental studies depends on the utilization of adequate sampling protocol and analytical method for obtaining reliable results and minimizing analytical uncertainties. In order to demonstrate the applicability of INAA for determining chemical element composition of invertebrates, this work evaluated sample representativeness in terms of subsampling and sample size. Br, Co, Fe, K, Na, Sc and Zn could be determined in very small samples despite increasing of analytical uncertainties. Special attention should be directed to invertebrate species with small structures because of the high chemical variation observed among different sample sizes tested.     

Metrological role of neutron activation analysis. IA. Inherent characteristics of relative INAA as a primary ratio method of measurement

In a series of three papers, the inherent characteristics of relative instrumental neutron activation analysis (INAA) as a primary ratio method of measurement, the unique functions of parametric INAA as an ideal back-up method of the relative INAA, and the valuable role of INAA in characterization of sampling behavior of individual elements in certified reference materials (CRMs) will be discussed. In this paper, the first of the series, the uncertainty evaluation and the traceability of values measured by neutron activation analysis (NAA), especially instrumental NAA (INAA), will be described to demonstrate the method at its ”the state-of-the-art” level can meet CCQM criteria for a primary ratio method. The scope and examples will be given. Received: 19 March 2001 Accepted: 2 October 2001     

NAA Study on Homogeneity of Reference Materials and their Suitability for Microanalytical Techniques

Homogeneity of the existing (Virginia Tobacco Leaves CTA-VTL-2 (ICHTJ), Apatite Concentrate CTA-AC-1 (ICHTJ), Fine Fly Ash CTA-FFA-1 (ICHTJ) and candidate certified reference materials (CRMs) (IAEA-338 Lichen, IAEA-413 Algae, Spruce Shoots RMF II (Germany)) was studied by neutron activation analysis (NAA). Several samples of small mass (ca. 1 or 10 mg) taken from various containers were analyzed by instrumental NAA and the results for several elements were compared by Fisher's test and t-test with analogous series of results for samples taken from one container. In the second approach, sampling variance was estimated for some elements from overall variance and the components of analytical variance. The results were interpreted with the aid of Ingamells' sampling constant. Particle size distribution of the reference materials was also measured by several techniques. In addition quantitative determinations for some elements were performed and results compared with the certified values. The results of the present study were discussed with reference to suitability of CRMs to microanalytical techniques. It was pointed out that the term "microanalysis" itself is not always unequivocally understood and used.     

X-ray fluorescence spectrometry for high throughput analysis of atmospheric aerosol samples: The benefits of synchrotron X-rays

The determination of trace element mass concentrations in ambient air with a time resolution higher than one day represents an urgent need in atmospheric research. It involves the application of a specific technique both for the aerosol sampling and the subsequent analysis of the collected particles. Beside the intrinsic sensitivity of the analytical method, the sampling interval and thus the quantity of collected material that is available for subsequent analysis is a major factor driving the overall trace element detection power. This is demonstrated for synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) of aerosol samples collected with a rotating drum impactor (RDI) in hourly intervals and three particle size ranges. The total aerosol mass on the 1-h samples is in the range of 10 µg. An experimental detection of the nanogram amounts of trace elements with the help of synchrotron X-rays was only achievable by the design of a fit-for-purpose sample holder system, which considered the boundary conditions both from particle sampling and analysis. A 6-µm polypropylene substrate film has evolved as substrate of choice, due to its practical applicability during sampling and its suitable spectroscopic behavior. In contrast to monochromatic excitation conditions, the application of a ‘white’ beam led to a better spectral signal-to-background ratio. Despite the low sample mass, a counting time of less than 30 s per 1-h aerosol sample led to sufficient counting statistics. Therefore the RDI-SR-XRF method represents a high-throughput analysis procedure without the need for any sample preparation. The analysis of a multielemental mass standard film by SR-XRF, laboratory-based wavelength-dispersive XRF spectrometry and laboratory-based micro XRF spectrometry showed that the laboratory-based methods were no alternatives to the SR-XRF method with respect to sensitivity and efficiency of analysis.     

Accurate measurement of bromine contents in plastic samples by instrumental neutron activation analysis

Accurate measurements of bromine contents in plastic samples were made by the direct comparator instrumental neutron activation analysis (INAA). Individual factors affecting the measurements were comprehensively evaluated and compensated, including the volatility loss of bromine from standard comparators, the background bromine level in the filter papers used for preparation of the standard comparators, nuclear interference, γ-ray spectral interference and the variance among replicates of the samples. Uncertainty contributions from those factors were thoroughly evaluated and included in the uncertainty budgeting of the INAA measurement. ⁸¹Br was chosen as the target isotope, and the INAA measurements for bromine were experimentally confirmed to exhibit good linearity within a bromine content range of 10–170 μg. The established method has been applied to the analysis of eight plastic samples: four commercially available certified reference materials (CRMs) of polyethylene and polystyrene and four acrylonitrile butadiene styrene (ABS) samples prepared as the candidate reference materials (KRISS CRM 113-01-012, -013, -014 and -015). The bromine contents of the samples were calculated at three different γ-ray energies and compared, showing good agreement. The results of the four CRMs also showed good consistency with their certified values within the stated uncertainties. Finally, the bromine contents of the ABS samples were determined with expanded uncertainties (at a 95% level of confidence) between 2.5% and 5% in a bromine content range of 25–900 mg kg⁻¹.     

Reference materials for small-sample analysis

Many modern analytical techniques use small solid samples and lack proper reference materials for their calibration and quality assurance. A remedy to this deficiency may be in the development of a new genre of highly homogeneous natural matrix materials, their properties being studied with analytical techniques such as PIXE and μ-PIXE, solid sampling AAS, scanning electron microscopy in combination with electron probe X-ray microanalysis, and INAA. Suitable natural materials may be obtained in form of single cell biological materials, finely dispersed suspensions and precipitates such as air particulate matter or sediments, and by appropriate particle size reduction of complex matrices. Initial studies have been carried out on single cell green algae biomass and air particulate matter, as well as several processed materials. Narrow particle size distributions with particles preferably below 10 μm diameter may assure the desired analytical homogeneity. The determination of sampling parameters for individual measurands will ascertain the utility of a material for small-sample analysis. Received: 16 June 1997 / Revised: 24 September 1997 / Accepted: 27 September 1997     

A new certified reference material for benzene measurement in air on a sorbent tube: development and proficiency testing

A certified matrix reference material (CRM) for the measurement of benzene in ambient air has been developed at Laboratoire National de Métrologie et d’Essais. The production of these CRMs was conducted using a gravimetric method fully traceable to the International System of Units. The CRMs were prepared by sampling an accurate mass of a gaseous primary reference material of benzene, using a high-precision laminar flowmeter and a mass flow controller, with a PerkinElmer sampler filled with Carbopack™ X sorbent. The relative standard deviations obtained for the preparation of a batch of 20 tubes loaded with 500 ng of benzene were below 0.2%. Each CRM is considered independent from the others and with its own certified value and an expanded uncertainty estimated to be within 0.5%, lower than the uncertainties of benzene CRMs already available worldwide. The stability of these materials was also established up to 12 months. These CRMs were implemented during proficiency testing, to evaluate the analytical performances of seven French laboratories involved in benzene air monitoring.     

Use of INAA,PGAA, and RNAA to determine 30 elements for certification of an SRM: Tomato Leaves, 157a

Analyses for certification have been made for the determination of 30 elements in the National Institute of Standards and Technology (NIST) Tomato Leaves renewal reference material, SRM 1573a. Three of the analytical techniques used were instrumental neutron activation analysis (INAA), radiochemical neutron activation analysis (RNAA), and prompt gamma activation analysis (PGAA). These techniques provided data on 19 elements by INAA, 10 elements by PGAA, and 7 elements by RNAA, with some overlap between techniques. For example, INAA was able to obtain overall analytical uncerainties (at the 95% confidence level) averaging ±2.2% for major and minor constituents (Ca, Mg, K), ±3.3% for constituents from 1 to 1000 g/g (Na, Fe, Al, Mn, Ba, Zn, Rb, La, Cr), and ±6.4% for elements between 10 and 1000 ng/g (Co, V, Se, Th, Sc, Sb), using sample dry weights of approximately 150 mg. These analyses represent the most extensive use to date of nuclear analytical techniques in the certification of a trace element SRM at NIST.     

金属组学：高通量分析技术进展与展望

金属组学是系统研究一种细胞、组织或完整生物体内全部金属原子的分布、含量、化学种态及其功能的新兴综合学科,它的提出受到人们越来越多的关注。本文综述了金属组学的研究方法,并对各种方法的特点和局限性做了比较说明．ICP-MS与NAA技术可实现多元素同时定量分析,同步辐射微束CT及μRF,EDX,PIXE,SIMS及LA-ICP—MS亦可实现金属组分布研究．金属组学研究目前正处于发展初期,仍有许多困难特别是分析仪器及方法方面的问题有待解决．已有的金属组形态及结构分析工作大多数采用的是较低效率的分析方法,一些正在发展中的关键技术平台,如HTXAS可真正实现高通量的形态或结构分析．此外,生物信息学有望成为金属组学研究的重要工具之一．     

Nuclear techniques applied to air particulate matter studies

The most important fraction of aerosols with respect to human health is the respirable fraction, which has particles less than 10 m in equivalent aerodynamic diameter (EAD), the so called PM 10 fraction. The collection of these respirable particles and the determination of their trace element composition is the focus of an IAEA Co-ordinated Research Programme (CRP). The IAEA Laboratory participated in this Programme and established collection sites for the air particulate samples on the grounds of the Atominstitute of the Austrian Universities in Vienna and the IAEA Laboratories, Seibersdorf, representing an urban residential site and a rural site. The collected samples as well as samples of simulated air filters (used also for blind controls) and control materials were analyzed sequentially and/or in sections by X-ray fluorescence (XRF), proton induced X-ray emission (PIXE), instrumental neutron activation analysis (INAA), and atomic absorption spectrometry (AAS). Results demonstrate the applicability of the PM-10 sampling approach, provided PIXE and/or INAA are used in the determinations. Reliable results can be obtained that will lead in comparable air pollution data for many regions in the world through CRP.     

Single-particle characterization of “Asian Dust” certified reference materials using low-Z particle electron probe X-ray microanalysis

In order to clearly elucidate whether Asian Dust particles experience chemical modification during long-range transport, it is necessary to characterize soil particles where Asian Dust particles originate. If chemical compositions of source soil particles are well characterized, then chemical compositions of Asian Dust particles collected outside source regions can be compared with those of source soil particles in order to find out the occurrence of chemical modification. Asian Dust particles are chemically and morphologically heterogeneous, and thus the average composition and the average aerodynamic diameter (obtainable by bulk analysis) are not much relevant if the chemical modifications of the particles must be followed. The major elemental composition and abundance of the particle types that are potential subjects of chemical modification can only be obtained using single-particle analysis. A single particle analytical technique, named low-Z particle electron probe X-ray microanalysis (low-Z particle EPMA), was applied to characterize two certified reference materials (CRMs) for Asian Dust particles, which were collected from a loess plateau area and a desert of China. The CRMs were defined by bulk analyses to provide certified concentrations for 13 chemical elements. Using the low-Z particle EPMA technique, the concentrations of major chemical species such as aluminosilicates, SiO₂, CaCO₃, and carbonaceous species were obtained. Elemental concentrations obtained by the low-Z particle EPMA are close to the certified values, with considering that the single particle and bulk analyses employ very different approaches. There are still some discrepancies between those concentration values, resulting from analyses of particles with different sizes, different sample amounts analyzed, and uncertainties involved in the single particle analysis.     

Comparison of relative INAA and k 0-INAA using soil and sediment reference materials

The objective of this work was to compare the results obtained by the relative INAA and k ₀-INAA methods for the same input parameters (sample mass, nuclear data, net peak area for the same gamma line and the same measurement and same cooling and measurement times). In total eight environmental soil and sediment reference materials (RM) or certified reference materials (CRM) from different producers were analysed. In this work only the recommended or certified values were considered, allowing comparison of the two methods for 30 elements. The results point out that k ₀-INAA possesses superior qualities compared to relative INAA, being insensitive to flux gradients, and independent of recommended/certified values in RMs/CRMs, often used as standards in relative INAA.