Solvent Extraction Studies of Gadolinium in Tri-Butyl Phosphate

Fast reactor spent fuel reprocessing plants should be designed for inherent criticality safety due to high plutonium content. Addition of soluble neutron poison is one way to do that. Gadolinium is the best choice based on neutron absorption cross section and chemical compatibility. In this work, using classical thermodynamic approach, the distribution coefficient of gadolinium in tributyl phosphate has been calculated and compared with the experimental data. The influence of acidity and uranium at equilibrium on gadolinium distribution in tributyl phosphate has been investigated. The result establishes the feasibility of employing gadolinium as soluble neutron poison in fast fuel reprocessing.     

Determination of chromium,manganese, lead and cadmium in biological samples including hair using direct electrothermal atomic absorption spectrometry

Direct analysis of solid samples employing a laboratory assembled electrothermal atomic absorption spectrometer is demonstrated to be a feasible approach for determination of trace elements in plant tissue and hair samples for special applications in plant physiology and biomedical research. As an example, the kinetics of Cr uptake by cabbage and its distribution have been measured as a function of chromium speciation in the nutrient solution. Further, longitudinal concentration gradients of Cr, Pb and Cd have been measured in hair of various population groups exposed to different levels of these elements in ambient and/or occupational environments. The techniques are validated for the determination of these trace elements by neutron activation analysis, dissolution atomic absorption spectrometry and by analysis of certified reference materials. Slurry sample introduction is found appropriate for routine trace element determination and in homogeneity testing. Direct sample introduction is indispensable in the analysis of very small (< 1 mg) tissue biopsy samples in the determination of trace element distributions.     

微波消解-电感耦合等离子体质谱(ICP-MS)法测定板栗中的矿物元素及稀土元素

为了准确测定板栗中矿物元素和稀土元素的含量水平,采用冷冻干燥方式预处理样品,选用硝酸和过氧化氢体系微波消解样品,结合电感耦合等离子体质谱技术,建立了板栗中钠(Na)、钾(K)、镁(Mg)、锰(Mn)、铁(Fe)、钒(V)、钴(Co)等19种矿物元素及镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)等15种稀土元素的同时分析测定方法。方法检出限为0.0027~0.78μg/L,相对标准偏差为1.4%~6.3%。通过国家标准物质GBW10019苹果的准确度实验验证,测定结果均在标准证书值范围内。实验结果表明,方法适用于板栗中矿物元素及稀土元素的同时测定。     

Synthesis of novel texaphyrins containing lanthanides and boron

Texaphyrin macrocycles that contain gadolinium or lutetium, such as motexafin gadolinium and motexafin lutetium, are versatile anticancer therapeutics and diagnostics. Gadolinium texaphyrins substituted with carborane clusters could also find application in combined gadolinium and boron neutron capture therapy (GdB-NCT). The synthesis and characterization of novel texaphyrins containing gadolinium or lutetium in the pentaaza core and two carborane clusters bound to opposite pyrrol units of the macrocycle are described.     

Atmospheric deposition of heavy metals in Norway studied by the analysis of moss samples using neutron activation analysis and atomic absorption spectrometry

In a study of the atmospheric deposition of trace elements in different parts of Norway, samples of the mossHylocomium Splendens were analyzed with respect to 28 elements. The determination of Cu, Zn, Cd, and Pb was carried out by atomic absorption spectrophotometry, while 24 additional elements were determined by instrumental neutron activation analysis. In samples from southernmost Norway, a substantially higher concentration was found for elements such as Pb, Sb, V, Cr, Cu, Zn, As, Se, Mo, Ag, and Cd than in samples from places located in the more northerly parts of the country. The results indicate that sources which are to the south and south-west of Scandinavia, contribute significantly to heavy metal deposition in Norway.     

Capillary neutron optics for prompt-gamma activation analysis

A neutron lens has been constructed to focus cold neutrons from the exit of a⁵⁸Ni neutron guide, which delivers a beam to the Prompt-Gamma Activation Analysis (PGAA) station at the NIST Cold Neutron Research Facility. The lens compresses a neutron beam of cross section 50 mm× 45 mm onto a focal spot of diameter 0.53 mm (fwhm) wich an average gain of 80 in neutron current density. PGAA measurements have been performed to demonstrate the enhanced sensitivity and detection limits for various elements and the spatial resolution in one transverse dimension. For the two test particles (a gadolinium glass bead and cadmium metal of sizes less than 0.5 mm), the gain in the -count rate with the lens is a factor of 60, and the detection limit is improved by a factor of 20. The system can be used for two-dimensional mapping of samples on a sub-millimeter scale to complement other analytical techniques such as neutron depth profiling (NDP).     

Determination of Fe,Nb and Si in titanium (IV) oxide white pigments by AAS using multivariate linear calibration methods

Models for the quantitative determination of Fe, Nb and Si in titanium (IV) oxide white pigments by flame atomic absorption spectrometry (AAS) are described. For the models two multivariate linear calibration techniques have been used: principal component regression (PCR) and partial least squares (PLS1). Absorbances measured at wavelengths for elements present in solution have been considered as independent (x) variables, while the concentrations of elements (or their oxide) to be determined have been taken as dependent (y) variables. The results obtained by the models do not differ significantly (alpha=0.05) from those achieved by the XRF method checked in advance by another independent method, the neutron activation analysis (NAA).     

Trace metals in human lung as determined by neutron activation analysis of bronchoalveolar lavage

The possibility to use the bronchoalveolar lavage (BAL) in combination with analytical methods for trace metal analysis such as neutron activation analysis (NAA), inductively coupled plasma (ICP) and electrothermal atomic absorption spectroscopy (ETASS) for the determination of trace elements in the lung of living subjects has been investigated. In particular more than 30 elements have been determined: (1) in physiological solutions used for bronchopulmonary lavage (blank values) (2) in BALs of volunteer patients (unexposed subjects) (3) in BALs of occupational workers affected by pulmonary fibrosis as diagnosed by clinical methods (exposed subjects). Although the number of cases with metal exposure studied by NAA-BAL method is too limited to draw definitive conclusions the results suggest that the procedure can provide interesting qualitative information on metals which would be actually retained in the lung tissue. However, although the method may become of importance when integrated with clinical examinations further investigations are necessary to establish qualitative relations between trace metal levels determined in the BAL and the total elemental content of the lung tissue.     

Instrumental neutron activation determination of Pt,Ru, Ir,Sc, Cr,Fe, Co,La, Ce,Nd, Sm,Yb, Lu,Hf and Ta employing CIRUS reactor as a thermal neutron source

An accurate and simple method has been developed for the determination of Pt, Ru, Ir and other elements employing instrumental neutron activation analysis (INAA). Nondestructive analysis has been carried out for the determination of these elements in different rock samples such as Dolerite, Dyke Dolerite, Country Basalt, Hyaloclastite, Trachyte, Ijolite, Spillite, Diorite and Lamprophyre from various locations like Daman, Tapti, Murud, Talasari, Ranala and Bassein in Maharashtra state. High flux provided by the CIRUS reactor (1×10¹³ n cm^?2s^?1) has been used for thermal neutron bombardment followed by radioassaying of the (n,γ) products on a HPGe detector coupled to a PC-based MCA unit.     

The Rapid and Non-Destructive Determination of Vanadium in Carbons by the Neutron Activation Analysis Using Gadolinium as an Internal Standard Material

Abstract

The present work deals with the determination of vanadium in high grade carbons by the thermal neutron activation using a Van de Graaff Accelerator. In this study, gadolinium oxide is used as the internal standard material, and the detection limit of this method is c. a. 1 ppm.     

Isotopes as tracers in analytical chemistry

A survey is given of the availability of radioactive and of concentrated heavy isotopes in Holland and of the instruments for their measurements.The principles of the application of tracers in analytical chemistry are reviewed and examples of the different kinds are described. Finally the determination of elements by induced radioactivity and by neutron absorption is dealt with.     

Forty-five years of neutron activation analysis in Slovenia: achievements towards improved quality of measurements results

Main achievements towards improved quality of measurements results obtained by neutron activation analysis (NAA) at the TRIGA Mark II reactor of the Jožef Stefan Institute during its 45 years of continuous operation are reviewed from a historical perspective; emphasis is on the features specific for NAA. The development of radiochemical neutron activation analysis for characterising reference materials is described in detail in the first part. Several approaches specific for the method such as the determination of long-lived radionuclides, the simultaneous determination of several elements using double irradiation and the internal standard method are presented in more detail. Several interesting approaches such as combination with liquid scintillation counting detection and combination with radiometric measurements are outlined. Then, the development of instrumental neutron activation analysis, specifically the k ₀-NAA based method is discussed. The contribution towards methodological development of uncertainty assessment is outlined, and the importance of the nuclide-specific and neutron fluence-specific approach is emphasised. Throughout the paper, the importance of neutron activation analysis and contributions of measurements results obtained by this method to characterising (candidate) reference materials is shown.     

Synchrotron X-ray and Neutron Diffraction Studies in Solid-State Chemistry

Neutron diffraction studies, especially with powders, play an important role in structural solid-state chemistry, making possible the precise determination of the location of light atoms, particularly hydrogen, and enabling a distinction to be made between certain neighboring elements in the periodic table that are difficult to distinguish in experiments with X-rays. Neutron diffraction investigations also make a unique contribution in the area of magnetic structure determination. The availability of intense synchrotron X-rays sources, however, is opening up new opportunities to the structural chemist, many of them complementary to the “traditional” strengths of neutron methods. The key features of synchrotron radiation in relation to structural studies are the wavelength tunability, which facilitates the use of resonant diffraction methods, and the high brightness and excellent vertical collimation of the source, which make possible the construction of diffractometers with unparalleled angular and spatial resolution. The following types of experiments are now possible with synchrotron X-ray diffraction: (1) The ab initio determination of structures from powder diffraction data. (2) The differentiation between different oxidation states of an element (valence contrast experiments) based upon the sensitivity of an absorption edge to the valence of the element in question. (3) The differentiation of elements adjacent to each other in the periodic table, which is now feasible with synchrotron X-rays for all elements beyond chromium. (4) Site-selective X-ray absorption spectroscopy. (5) The study of cation occupancies in materials where more than one element occupies a site that is, or may be, partially occupied. (Such problems are important in zeolite chemistry and high-temperature superconductors.) (6) The determination of crystal structures from microcrystals. (7) In situ and rapid, time-resolved diffraction studies. This review examines the roles played by X-ray and neutron diffraction studies in modern solid-state chemistry, and describes some recent examples in which the use of neutron radiation or synchrotron X-rays has been advantageous.     

Accurate determination of the noble metals II. Determination methods

As was shown in the first part of this contribution, accurate analytical determination of the noble metals in rocks, ores and alloys needs a sophisticated sample pretreatment prior to the final determination step of the preconcentrated elements. For this many instrumental and classical methods are available, the choice of which is usually dictated by levels of precious metal to be handled, nature of sample matrix and availability of the instruments. For trace levels (μg/g range) flame atomic absorption and inductively coupled plasma (ICP) emission spectrometry can be used. ICP emission is favoured because of ease of multi-element operation. At the sub-μg/g level furnace atomic absorption and nuclear techniques (mainly neutron activation) are favoured. Minor and % concentrations are best handled by X-ray fluorescence. The use of standard reference samples and internal and external laboratory control schemes are essential to the accurate determination of precious metals.     

Rapid analysis of biological reference materials by instrumental neutron activation

Summary Instrumental neutron activation analysis (INAA) was applied to the rapid determination of cadmium and other elements in the IAEA biological reference material horse-kidney (H-8). Nuclear reactor neutrons and epithermal neutrons were used as neutron sources. Cadmium, bromide, iodine and phosphorus were determined by epithermal neutron activation analysis. Aluminum was determined by reactor neutron activation analysis taking into account the contribution of phosphorus to the ²⁸Al activity.     

Preconcentration and instrumental neutron activation analysis of acid rain for trace elements

A combination of instrumental and preconcentration neutron activation analysis (NAA) methods has been developed for multielement determination in acid rain. Concentrations of 24 elements have been measured in the particulate matter of rainwater by the instrumental NAA method which involves 3 irradiation and 4 counting periods. Trace elements in the soluble fraction of rainwater have been preconcentrated using Chelex-100 resin. Various factors that could influence the retention of elements on to the resin have been examined, and reagent and other blanks investigated in detail. Concentrations of 15 elements have been measured by directly irradiating the resins. A graphite furnace atomic absorption spectrometry method has been used for determining Cd and Pb levels in the soluble fraction. Precision and accuracy of the methods have been evaluated, and limits of detection and determination calculated. The methods have been applied to rainwater samples collected from 36 locations across Canada. Enrichment factors, interelement and inter-ion concentration correlation coefficients are discussed     

Determination of Fe, Nb and Si in titanium (IV) oxide white pigments by AAS using multivariate linear calibration methods

Models for the quantitative determination of Fe, Nb and Si in titanium (IV) oxide white pigments by flame atomic absorption spectrometry (AAS) are described. For the models two multivariate linear calibration techniques have been used: principal component regression (PCR) and partial least squares (PLS1). Absorbances measured at wavelengths for elements present in solution have been considered as independent (x) variables, while the concentrations of elements (or their oxide) to be determined have been taken as dependent (y) variables. The results obtained by the models do not differ significantly (=0.05) from those achieved by the XRF method checked in advance by another independent method, the neutron activation analysis (NAA).     

Trace element analysis of airborne particulate matters in relation to air pollution in Benin City, Nigeria

The methods of neutron activation analysis (NAA) and atomic absorption spectrometry (AAS) have been employed to determine the concentration levels of 18 trace elements in filter-collected airborne aerosols over an urban area in Nigeria. The highest concentrations measured in the samples were for Cl, Na, Al, Pb, Ca and Zn. The aerosol particles were found to contain higher concentrations of soil-derived trace elements, such as Al, Ti, K and Na than those derived from combustion and industrial activities such as As, Cd, Mn, Zn, Pb, Ni and Sb. The average precision of measurements varied between +/- 5.2% and 13% for most elements. Possible sources of the elements are also discussed.     

Neutron activation analysis of Urartian pottery from eastern Anatolia

The assessment of environmental pollution of the coastal areas of the Malaysian Peninsula was done by analyzing the contents of the heavy and trace elements in the bivalves blood clams (Anadara granosa) and green mussels (Perna viridis) and sediments at twenty-two sampling stations to look for prevailing trends. Heavy and trace elements analyzed in this study were As, Cd, Cr, Cu, Pb, Se and Zn. Two techniques, namely the neutron activation analysis (NAA) and atomic absorption spectrophotometry (AAS) were used in the quantitative determination of the heavy metals while Marine Sediment Reference Material (BCSS) and Lobster Hepatopancreas (TORT-1) provided the certified reference materials in the quality assurance control. The potential use of these bivalves as suitable bio-indicators was evaluated from correlation tests based on the concentrations of heavy and trace elements in the sediment-metals system to those in the bivalves.     

Determination of trace elements by neutron activation analysis using dinonylnaphthalene sulfonic acid as a preconcentrating agent

Dinonylnaphthalene sulfonic acid (HD) has been used as a preconcentrating agent to enrich trace metal ions and to separate the interfering elements such as Na, K, Cl and Br which normally exist in the natural aqueous systems. Experiments were performed by extracting the ions in the aqueous medium with HD in n-hexane and subsequently back-extracted into a minimal volume of acid solution. Factors influencing the extraction efficiency of the ions of interest were investigated. The preconcentration technique developed in this study was applied to the determination of trace elements in biological and natural water samples by neutron activation analysis.