Uranium enrichment measurements using the intensity ratios of self-fluorescence X-rays to 92 keV gamma ray in UXKα spectral region

In this paper, the known multigroup γ-ray analysis method for uranium (MGAU) as one of the non-destructive γ-ray spectrometry methods has been applied to certified reference nuclear materials (depleted, natural and enriched uranium) containing ²³⁵U isotope in the range of 0.32-4.51% atom ²³⁵U. Its analysis gives incorrect results for the low component ²³⁵U in depleted and natural uranium samples where the build-up of the decay products begins to interfere with the analysis. The results reveal that the build-up of decay products seems to be significant and thus the algorithms for the presence of decay products should be improved to resulting in the correct enrichment value. For instance, for the case of ²³⁵U analysis in depleted uranium or natural ore samples, self-induced X-rays such as 94.6 keV and 98.4 keV lying in UXK_α spectral region used by MGAU can be excluded from the calculation. Because the significant increases have been observed in the intensities of uranium self-induced X-rays due to γ-ray emissions with above 100 keV energy arising from decay products of ²³⁸U and ²³⁵U and these parents. Instead, the use of calibration curve to be made between the intensity ratios of self-fluorescence X-rays to 92^* keV γ-ray and the certified ²³⁵U abundances is suggested for the determination of ²³⁵U when higher amounts of decay products are detected in the γ-ray spectrum acquired for the MGAU analysis.     

Precise determination of dissolved silica in seawater by ion-exclusion chromatography isotope dilution inductively coupled plasma mass spectrometry

Ion exclusion chromatograph (IEC) isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP–MS) (IEC–ID–ICP–MS) was developed for measurement of dissolved silica in seawater, which was applied to production of certified reference materials (CRMs) of three concentration levels of nutrients (high, medium and low levels). IEC–ICP–MS has been employed to separate dissolved silica from seawater matrix. In the present study, in order to solve substantial problems due to spectral interference in ICP–MS and to improve the accuracy of IEC–ICP–MS beyond standard addition or conventional calibration methods, ID method was coupled with ICP-sector field mass spectrometry (operated under medium resolution,i.e., m/Δm = 4000). In addition, effects of various operating parameters in ICP–MS on a silicon background level were also investigated to obtain lower background equivalent concentration (BEC). As a result, 3 ng g⁻¹ of the BEC and 0.5 % of relative standard uncertainties were achieved in the analyses of dissolved silica in seawater samples at concentration levels from 4.0 mg kg ^-1 to 0.8 mg kg⁻¹ as silicon. The developed method was successfully validated by analyses of an artificial seawater containing a known amount of silicate and the seawater certified reference material MOOS-2 produced by the National Research Council Canada.     

Electrothermal atomic absorption spectrometric determination of vanadium in extracts of soil and sewage sludge certified reference materials after fractionation by means of the Communities Bureau of Reference modified sequential extraction procedure

A modified three-step sequential extraction procedure proposed by the Commission of European Communities Bureau of Reference (BCR) was applied to certified reference materials of three different soil groups (rendzina, luvisol, cambisol) and sewage sludge of different composition originating from a municipal water treatment plant in order to assess potential mobility and the distribution of vanadium in the resulting fractions. Analysis of the extracts was carried out by electrothermal atomic absorption spectrometry with Zeeman background correction using transversely heated graphite atomizers. Extracts showed significant matrix interferences which were overcome by the standard addition technique. The original soil and sludge certified reference materials (CRMs) and the extraction residue from the sequential extraction were decomposed by a mixture of HNO₃–HClO₄–HF in an open system. The content of V determined after decomposition of the samples was in very good agreement with the certified total values. The accuracy of the sequential extraction procedure was checked by comparing the sum of the vanadium contents in the three fractions and in the extraction residue with the certified total content of V. The amounts of vanadium leached were in good correlation with the certified total contents of V in the CRMs of soils and sewage sludge. In the soils examined, vanadium was present almost entirely in the mineral lattice, while in the sewage sludge samples 9–14% was found in the oxidizable and almost 25% in the reducible fractions. The recovery ranged from 93–106% and the precision (RSD) was below 10%.     

Use of INAA in the preparation of a set of soil reference materials with certified values of total element contents

A set of certified Reference Materials was prepared consisting of four natural agricultural soils with normal (n) and elevated (e) levels of element contents: CRM 7001 Light Sandy Soil (n), CRM 7002 Light Sandy Soil (e), CRM 7003 Silty Clay Loam (n), and CRM 7004 Loam (e). In these materials, certified and/or information values of the total contents of the elements As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, V and Zn, and their fractions extractable by aqua regia, boiling and cold 2M nitric acid were derived from an interlaboratory comparison in which 28 laboratories participated. Highly precise and accurate procedures of instrumental neutron activation analysis (INAA) were employed for homogeneity testing and also for certification of the total element contents. For comparation purposes, NIST SRM-2704 Buffalo River Sediment was analyzed by INAA, as well. The INAA results obtained compared very well with the certified and/or information values for four soil CRMs and also with NIST values for SRM-2704. From this agreement, a very high reliability of the new soil CRMs can be inferred.     

RNAA in metrology: A highly accurate (definitive) method

The idea of highly accurate (definitive) methods by radiochemical neutron activation analysis (RNAA) is presented and illustrated with several examples of methods worked out in this Laboratory over the past several years. Definitive methods by RNAA are constructed by combining reactor neutron activation with very selective and quantitative post-irradiation separation of the indicator radionuclide by column chromatography followed by γ-ray spectrometric measurement. All conditions for the determination of the individual element are optimized and uncertainties associated with every step of the analytical procedure are minimized. Even after the method has been thoroughly elaborated and validated through the analysis of appropriate certified reference materials (CRMs), the results obtained in each series of measurements are acknowledged as obtained by definitive method only when a series of previously formulated criteria is simultaneously fulfilled. The examples of definitive methods for the determination of cadmium, cobalt and molybdenum, respectively, in biological materials are presented. Each of these methods has detection limit of the order of ng g⁻¹ or better, and yields accurate and precise results. The expanded standard uncertainty is of the order of 2.6% for the case of single-element determination (Co) and 3.4-5.2% for the less favourable case (Mo) where there is necessity for simultaneous determination of uranium to correct for interference due to fission reaction. Definitive methods by RNAA may constitute an option or alternative with respect to ID-MS as methods of “guaranteed accuracy” being also a perspective solution in the case of monoisotopic elements, for which ID-MS cannot be used.     

Development of a miniature dielectric barrier discharge–optical emission spectrometric system for bromide and bromate screening in environmental water samples

Dielectric barrier discharge (DBD) at atmospheric pressure provides an efficient radiation source for the excitation of bromine and it is used for the first time for optical emission spectrometric (OES) detection of bromide and bromate. A portable DBD–OES system is developed for screening potential pollution from bromide and bromate in environmental waters. Bromide is on-line oxidized to bromine for in-situ generation of volatile bromine. Meanwhile, a helium stream carries bromine into the DBD micro-plasma for its excitation at a discharging voltage of 3.7 kV and optical emission spectrometric detection with a QE65000 charge-coupled device (CCD) spectrometer in the near-infrared spectral region. Similarly, the quantification of bromate is performed by its pre-reduction into bromide and then oxidized to bromine. The spectral characteristics and configuration of the DBD micro-plasma excitation source in addition to the oxidation vapor generation of bromine have been thoroughly investigated. With a sampling volume of 1 mL, a linear range of 0.05–10.0 mg L⁻¹ is obtained with a detection limit of 0.014 mg L⁻¹ by measuring the emission at 827 nm. A precision of 2.3% is achieved at 3 mg L⁻¹ bromide. The system is validated by bromine detection in certified reference material of laver (GBW10023) at mg L⁻¹ level, giving rise to satisfactory agreement. In addition, it is further demonstrated by screening trace bromide and bromate as well as spiking recoveries in a series of environmental water samples.     

Primary standards in activation analysis

The availability of natural matrix reference materials evaluated for trace element content has resulted in their widespread use as standards (i.e., calibration materials; comparators) for instrumental neutron activation analysis (INAA). Due to the uncertainties associated with their certified values, the limited number available, and the relative matrix independence of INAA, these reference materials are more properly utilized as quality assessment materials, after calibration of the INAA analytical system with true primary standards. Terminology is defined, the use of matrix reference materials to evaluate the analytical system is discussed, techniques for the accurate preparation of primary standards for trace element analyses are reviewed, and necessary precautions in the accurate comparison of samples to standards are presented.     

Determination of mercurial species in fish by inductively coupled plasma mass spectrometry with anion exchange chromatographic separation

This work demonstrated the feasibility of mercury speciation analysis by anion exchange chromatographic separation with inductively coupled plasma mass spectrometry detection. For the first time, by complexing with the mobile phase containing 3-mercapto-1-propanesulfonate into negatively charged complexes, fast separation of inorganic mercury (Hg²⁺), monomethylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) was achieved within 5 min on a 12.5-mm strong anion exchange column. The detection limits for Hg²⁺, MeHg, EtHg and PhHg were 0.008, 0.024, 0.029 and 0.034 μg L⁻¹, respectively. The relative standard deviations of peak height and peak area (5.0 μg L⁻¹ for each Hg species) were all below 3%. The determined contents of Hg²⁺, MeHg and total Hg in a certified reference material of fish tissue by the proposed method were in good accordance with the certified values with satisfactory recoveries. The relative errors for determining MeHg and total mercury were −2.4% and −1.2%, respectively, with an acceptable range for spike recoveries of 94–101%. Mercury speciation in 11 fish samples were then analyzed after the pretreated procedure. The mercury contents in all fish samples analyzed were found compliant with the criteria of the National Standards of China.     

Speciation of the bio-available iodine and bromine forms in edible seaweed by high performance liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry

A bioavailability study based on an in vitro dialyzability approach has been applied to assess the bio-available fractions of iodine and bromine species from edible seaweed. Iodide, iodate, 3-iodo-tyrosine (MIT), 3,5-diiodo-tyrosine (DIT), bromide and bromate were separated by anion exchange chromatography under a gradient elution mode (175 mM ammonium nitrate plus 15% (v/v) methanol, pH 3.8, as a mobile phase, and flow rates within the 0.5–1.5 mL min⁻¹ range). Inductively coupled plasma-mass spectrometry (ICP-MS) was used as a selective detector for iodine (¹²⁷I) and bromine (⁷⁹Br). Low dialyzability ratios (within the 2.0–18% range) were found for iodine species; whereas, moderate dialyzability percentages (from 9.0 to 40%) were obtained for bromine species. Iodide and bromide were the major species found in the dialyzates from seaweed, although MIT and bromate were also found in the dialyzates from most of the seaweed samples analysed. However, DIT was only found in dialyzates from Wakame, Kombu, and NIES 09 (Sargasso) certified reference material; whereas, iodate was not found in any dialyzate. Iodine dialyzability was found to be dependent on the protein content (negative correlation), and on the carbohydrate and dietary fibre levels (positive correlation). However, bromine dialyzability was only dependent on the protein amount in seaweed (negative correlation).     

Synthesis of no-carrier-added 6-[11C]methyl-l-DOPA

Taking advantages of nuclear analytical techniques (NATs) with non-destruction, multielement capability, small and estimable uncertainties over a wide range of sample sizes, the sampling behavior of multielements for a home-made natural matrix material was studied with sample sizes ranging from several hundred mg down to tenths ng, namely nine orders of magnitude, by a combination of three NATs, neutron activation analysis (NAA), proton induced X-ray emission (PIXE) and synchrotron radiation X-ray flurescence (SR-XRF), in an effort to explore a procedure for the development of certified reference materials (CRMs) suitable for quality control of microanalysis. For accurately weighable sample sizes (>1?mg), sampling uncertainties for 13 elements were found to be less than 1% by INAA. For sample sizes unable to be accurately weighed (<1?mg), PIXE and SR-XRF were used, respectively. Sampling uncertainties were found to be less than 1% at sample sizes of tenth mg level for seven elements, and less than 10% on ng levels for three elements. Considering these three elements have satisfied homogeneity (sampling uncertainty less than 10%) at ng sample size level, any one of them can be served as a ??relative balance?? in sampling behavior characterization of multielements on sample size levels larger than ng (e.g., ??g level). On this basis, sampling uncertainties for nine elements were found to be less than 10% on ??g sample size level by INAA. The results indicate that the matrix is eligible as a candidate of CRMs suitable for quality control of solid sampling microanalysis.     

Certification of reference materials for Cd, Cr, Hg and Pb in polypropylene

Two reference materials, at relatively low and high concentrations (GBW08404 and GBW08405), for analysis of the mass fractions of Cd, Cr, Hg and Pb in polypropylene were developed. The reference materials were prepared by doping blank polypropylene base material with Cd, Cr, Hg and Pb in the form of oxides, salts or pigments. Homogeneity and stability studies were performed by inductively coupled plasma mass spectrometry. The certification of the four analytes was carried out by isotope-dilution mass spectrometry (IDMS) with microwave-assisted digestion. Combined uncertainties were calculated from the IDMS uncertainty evaluation budget and the uncertainty of the homogeneity. The mass fractions of Cd, Cr, Hg and Pb of the two certified reference materials (CRMs) were from 8 to 1,000 mg kg⁻¹. The two samples were also used in an interlaboratory comparison scheme in which National Institute of Metrology, China, National Metrological Institute of Japan and Korea Research Institute of Standards and Science participated. The agreement of the comparison results proved that the certification procedure of the CRMs is valid and that the certified values of Cd, Cr, Hg and Pb are accurate and reliable.     

Determination of aluminium contents in selected food samples by instrumental neutron activation analysis

Food and food products are the main sources of Aluminium entering the human body. In order to know aluminium contents in food and food products, selected 26 samples from local market were analyzed by instrumental neutron activation analysis (INAA) using reactor neutrons and high resolution gamma-ray spectrometry. INAA using 1,779 keV γ-ray of ²⁸Al (2.24 min) was used for aluminium concentrations in the range of 33–529 mg kg^?1. Two NIST standard reference materials (SRMs) and two IAEA reference materials (RMs) were analyzed by INAA for quantification of aluminium as a part of method validation.     

Inter-method comparison for the determination of antimony and arsenic in peat samples

Four analytical approaches, based on different physical principles, for the determination of antimony (Sb) and arsenic (As) in ancient peat samples were critically evaluated: (a) open vessel digestion/hydride generation-atomic absorption spectrometry (HG-AAS), (b) closed-pressurized digestion in a microwave oven followed by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS), (c) digestion in a microwave autoclave and subsequent quadrupole-inductively coupled plasma-mass spectrometry (Q-ICP-MS) measurements and (d) instrumental neutron activation analysis (INAA). The quality control scheme applied, always included the use of adequate plant reference materials to ensure the accuracy and precision of the analytical procedures. Additionally, two internal peat reference materials were analyzed using all four analytical approaches, generally showing good agreement for both elements. Method detection limits for As and Sb provided by all procedures were approximately 5 and 2 ng g⁻¹ which is sufficiently low for the reliable quantification of both elements in ancient, pre-anthropogenic peat samples. A comparison of As and Sb concentrations in a set of peat samples determined by INAA, HG-AAS and SF-ICP-MS revealed that INAA underestimated the values in a systematic manner, whereas HG-AAS and SF-ICP-MS data agreed very well. Best precision of the results was obtained by analytical procedures involving HG-AAS or Q-ICP-MS and varied from 3.6 to 4.3% and 7.1 to 7.5% for As (at about 0.5 μg g⁻¹) and Sb (at about 0.1 μg g⁻¹), respectively. The highest sample throughput (40 samples per run accomplished in 2 h) combined with low risk of sample contamination could be realized in the high-pressure microwave autoclave. The amount of sample required by all approaches was 200 mg, except for INAA which needed at least 25 times more sample mass to achieve comparable detection limits. For the quantification of As and Sb, inductively coupled plasma-mass spectrometry (ICP-MS) was preferred over INAA and HG-AAS, mainly because (a) less sample is needed and (b) As and Sb can be determined simultaneously. In addition, ICP-MS offers the possibility to measure concurrently a wide range of other elements which also are of environmental interest.     

Application of k0-based internal mono standard instrumental neutron activation analysis method method for composition analysis of stainless steel clad sample

The k₀-based internal mono standard instrumental neutron activation analysis (INAA) method was used for the composition analysis of some irregular shape stainless steel (SS) samples of type SS 316M, which is used as fuel cladding in Indian fast breeder test reactor (FBTR). The method utilizes in situ relative detection efficiency using γ-rays of the activation products present in the sample for overcoming γ-ray self-attenuation. Samples were neutron activated using the thermal column as well as the core position of the reactor and the assay of radioactivity was carried out by high-resolution gamma ray spectrometry. The elements determined were Fe, Cr, Ni, Mo, Mn, Co, Cu, As and W. Since all the major elements (Fe, Cr, Ni, Mo and Mn) were amenable to NAA, the relative elemental concentrations with respect to Fe, obtained by this method, were converted to their absolute values by mass balance. The results were compared with specified compositions and found to be satisfactory. In order to validate these results obtained by the standard-less approach, sub samples of SS 316M in solution forms were analyzed by prevalent relative and k₀ methods of INAA, and results were found to be in good agreement. The accuracy of the internal mono standard INAA method has been evaluated by analyzing an alloy steel certified reference material, CRM 225/1 of British Chemical Standards (BCS).     

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.     

Quality control with CRMs for trace element determination in candidate reference materials

Summary Three soil samples and five candidate materials of biological origin (bovine muscle, bovine kidney, bovine blood, rye flour and wheat flour) and one already certified RM (Bovine Liver, 12-02-01) were analyzed for their contents of Cd, Cu, Cr, Pb and Zn. Pressure digestion with nitric acid in PTFE (at 180°C) and quartz (at 290°C) vessels was used for sample decomposition. The measurements were made by graphite furnance atomic absorption spectrometry (ET-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and square wave voltammetry. The accuracy of analysis has been checked by simultaneous analyses of six similar CRMs. An excellent agreement between the found and certified values is illustrated by highly significant correlations.     

Microwave assisted extraction of iodine and bromine from edible seaweed for inductively coupled plasma-mass spectrometry determination

The feasibility of microwave energy to assist the solubilisation of edible seaweed samples by tetramethylammonium hydroxide (TMAH) has been investigated to extract iodine and bromine. Inductively coupled plasma-mass spectrometry (ICP-MS) has been used as a multi-element detector. Variables affecting the microwave assisted extraction/solubilisation (temperature, TMAH volume, ramp time and hold time) were firstly screened by applying a fractional factorial design (2^5-1 + 2), resolution V and 2 centre points. When extracting both halogens, results showed statistical significance (confidence interval of 95%) for TMAH volume and temperature, and also for the two order interaction between both variables. Therefore, these two variables were finally optimized by a 2² + star orthogonal central composite design with 5 centre points and 2 replicates, and optimum values of 200 °C and 10 mL for temperature and TMAH volume, respectively, were found. The extraction time (ramp and hold times) was found statistically non-significant, and values of 10 and 5 min were chosen for the ramp time and the hold time, respectively. This means a fast microwave heating cycle. Repeatability of the over-all procedure has been found to be 6% for both elements, while iodine and bromine concentrations of 24.6 and 19.9 ng g⁻¹, respectively, were established for the limit of detection. Accuracy of the method was assessed by analyzing the NIES-09 (Sargasso, Sargassum fulvellum) certified reference material (CRM) and the iodine and bromine concentrations found have been in good agreement with the indicative values for this CRM. Finally, the method was applied to several edible dried and canned seaweed samples.     

Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile–butadiene–styrene model samples and historical objects

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-μFTIR) was used to map photo-oxidative degradation of acrylonitrile–butadiene–styrene (ABS) and to investigate the presence and the migration of additives in historical samples from important Italian design objects. High resolution (3 × 3 μm²) molecular maps were obtained by FTIR microspectroscopy in transmission mode, using a new method for the preparation of polymer thin sections. The depth of photo-oxidation in samples was evaluated and accompanied by the formation of ketones, aldehydes, esters, and unsaturated carbonyl compounds. This study demonstrates selective surface oxidation and a probable passivation of material against further degradation. In polymer fragments from design objects made of ABS from the 1960s, UV-stabilizers were detected and mapped, and microscopic inclusions of proteinaceous material were identified and mapped for the first time.     

Conclusions from 13 years of stability testing of CRMs for determination of metal species

We present results of the systematic stability monitoring of certified reference materials (CRMs) for the mass fractions of metal species. Materials are tested regularly for the mass fractions of organotin, organomercury, organolead and organoarsenic species. Evaluation is based on ratios of results on samples stored under normal conditions and under even safer conditions (“reference stock”) to eliminate the effects of laboratory-to-laboratory variation. Of all results in this study, the results of organotin measurements show the highest relative standard deviations (up to 45%). Determination of methylmercury in sediment and fish is possible with much better precision (standard deviations of reproducibility below 5%). The accuracies of determinations of trimethyllead and organoarsenic species are slightly worse but still below 10%. The data confirmed stability since production (i.e. up to 13 years). However, shelf lives cannot be extended into the future based on these data, as uncertainty contributions for stability need to be included in the uncertainty budgets of CRMs to allow positive demonstration of the validity of certificates. Estimation of typical measurement uncertainties based on the data obtained from stability monitoring shows that potential degradation is negligible compared to uncertainties typical for this kind of measurement, demonstrating that the materials are still sufficiently reliable to demonstrate laboratory proficiency.     

Determination of gamma-globulin at nanogram levels by its enhancement effect on the resonance light scattering of functionalized HgS nanoparticles

A novel assay of γ-globulin (γ-IgG) with a sensitivity at the nanogram level is proposed based on the measurement of enhanced resonance light-scattering (RLS) signals resulting from the interaction of functionalized nano-HgS with γ-globulin. At pH 5.03, the RLS signals of functionalized nano-HgS were greatly enhanced by γ-globulin in the region of 200-700 nm characterized by the peak around 362 nm. Linear relationship can be established between the enhanced RLS intensity and γ-globulin concentration in the range of 10-140 ng ml⁻¹. The limit of detection is 2.71 ng ml⁻¹. Based on this, a new direct quantitative determination method for γ-globulin in blood serum samples without separation of human serum albumin (HSA) is established. The contents of γ-IgG in blood serum samples were determined with recovery of 95.7-102.5% and R.S.D. of 1.6-2.4%. This method is proved to be very sensitive, rapid, simple and tolerance of most interfering substances.