Activation analysis with charged particles

Activation methods are important because of their sensitivity. The accuracy and precision obtainable with charged-particle activation analysis (CPAA) have been significantly improved; the accuracy has been demonstrated in inter-laboratory and inter-method comparisons. The inherent complexity of CPAA makes it unsuitable for routine work, but the method is valuable for special applications, e.g., certification of reference materials, and for the determination of certain elements. Most applications concern the determination of light elements in metals and semi-conductor materials. After removal of surface layers by chemical etching, the concentrations of carbon, nitrogen and oxygen found by CPAA in some industrial metals, (e.g., aluminium, molybdenum and tungsten) proved to be orders of magnitude lower than expected from the results of other procedures. Other applications are the determination of medium- and high-Z elements, (e.g., calcium, cadmium, thallium and lead) in metals; these elements are very difficult to determine with neutron activation. Environmental powdered materials can be analyzed accurately; because of their low thermal conductivity, they must be irradiated under helium instead of vacuum to avoid volatilization of matrix components.     

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).     

Elemental analysis by gamma-ray detection following inelastic neutron scattering

A method of elemental analysis based on the detection of prompt γ-rays produced by the inelastic scattering of fast monoenergetic neutrons has been investigated. Time-of-flight discrimination techniques and the use of Ge(Li) detectors provide significant advances over previous studies. This method is multielemental, non-destructive, and essentially free of interferences and matrix effects. Sample analysis is rapid and selective excitation of various elements is possible. Many elements have been examined by this technique and minimum detection limits have been established. This method has been applied to the analysis of metal alloys.     

Total reflection X-ray fluorescence analysis of pollen as an indicator for atmospheric pollution

The viability of pollen is affected by environmental pollution and its use as a bio-indicator is proposed. Such effects can be observed and quantified by biological tests. However, a more accurate identification of the agents affecting the viability is required in order to validate the biological assay for environmental monitoring. The chemical analysis of pollen is meant to ascertain the existence of a correlation between its reduced biological functions and the presence of pollutants. Moreover, such biological systems act as accumulators and allow the detection and quantification of species present in the environment at low concentrations. Total reflection X-ray fluorescence analysis (TXRF) has been chosen for the investigation due to its high sensitivity, multielement capability and wide dynamic range. Corylus avellana L. (hazel) pollen has been collected in areas with different anthropic impact in the province of Trento, Italy. For the TXRF measurements, a liquid sample is needed, especially if a quantitative analysis is required. In the present work, the analysis after a microwave digestion has been compared with the analysis of a suspension of the pollen samples. In both cases, an internal standard has been used for the quantification. The concentrations of 17 elements ranging from Al to Pb have been determined in 13 samples. Analysis of the suspensions showed to be comparable to that of digested samples in terms of spectral quality, but the latter preparation method gave better reproducibility. Sub-ppm lowest limits of detection were obtained for iron and heavier elements detected.     

K-line X-ray fluorescence analysis of high-Z elements

X-ray fluorescence analysis with high-energy photons (typically 40–100 keV) is described. Measurement of K-lines from high-Z elements has attractive advantages, which are not available by L-line analysis in normal X-ray region. Through the comparison of excitation methods, it has been found that quasi-monochromatic beams with sufficient intensity and moderate spectral distribution are most suitable for improving the detection limit. Performances of other excitation methods and recent experimental trends are also discussed.     

Application of the Ko standardization method in neutron activation analysis of ceramic materials

An analytical procedure has been developed for neutron activation analysis of ceramic powders, it is mainly based on the application to the K_o standardization method and on the use of pelletizing for sample preparation. Precision and accuracy have been checked through the analysis of international standards. The procedure was applied to a commercial silicon carbide sample for the determination of 42 elements. Results were interpreted in terms of repeatability and accuracy by comparison to other trace analysis techniques. Additional short half-life elements were also determined by the K_o method.     

Instrumental neutron activation analysis of Obsidian rock

An instrumental neutron activation analysis technique has been developed for the simultaneous determination of up to 30 elements including major, minor and trace elements in Obsidian Rock (a proposed NBS-SRM-278). INAA method involves both short and long irradiations followed by gamma-ray activity measurement with a Ge(Li) detector. The accuracy of the procedure has been checked by analyzing IAEA Reference Materials.     

Destructive and nondestructive analysis of some elements in tissue and environmental samples by thermal neutron activation analysis technique

A rapid and selective method has been developed and applied for determining elements present in tissue and environmental samples by both destructive and nondestructive activation analysis. Nondestructive activation analysis involves the irradiation of the sample and standard of the elements such as Mn, Na, and K with thermal neutrons from²⁵²Cf neutron source followed by radioassay of the (n,r) products on a HPGe detector coupled to a PC-based MCA. Elements are determined by irradiating the samples in the thermal neutron flux of the CIRUS reactor and radiochemically separating the isotopes of interest using substoichiometric extraction and precipitation technique. The statistical evaluation of the method with respect to accuracy and precision of the method and its sensitivity are discussed.     

High-sensitive elemental analysis using multi-parameter coincidence spectrometer: GEMINI-II

In this study, using neutron activation analysis with multi-parameter coincidence method which was developed at Japan Atomic Energy Agency (JAEA), a non-destructive, ultra-high sensitive multi-elemental determination has been realized. The multi-parameter coincidence method is carried out with an array of 19 germanium detectors, GEMINI-II. Using this system, very weak γ-rays emitted from trace amounts of elements can be detected. The iridium concentration has been determined by means of neutron activation analysis with multi-parameter coincidence method for Cuban sediment samples across the K/T boundary strata.     

Measuremets of presolar grain in meteorite using neutron activation analysis with multi-parameter coincidence method

Neutron activation analysis with multi-parameter coincidence method was developed at the Japan Atomic Energy Agency (JAEA) and a non-destructive, ultra-high sensitive multi-elemental determination has been realized. The multi-parameter coincidence method is carried out with an array of 19 germanium detectors, GEMINI-II. Using this system, very weak γ-rays emitted from trace amounts of elements can be detected. The presolar grains were extracted from the Allende meteorite. Trace elements in the presolar diamonds were measured by neutron activation analysis with multi-parameter coincidence method.     

A scheme for the analysis of monazite and monazite concentrates

A scheme using ion-exchange methods is described for the analysis of monazites and monazite concentrates. The sample is opened up with concentrated sulphuric acid, and the resultant solution is applied to a column of Zeocarb 225 resin. After phosphate has been washed out, lead, aluminium, titanium, iron, uranium, calcium and magnesium are eluted with N hydrochloric acid and determined by specific, mainly spectrophotometric, methods. Rare earth elements are eluted with 3 N hydrochloric acid. Cerium is separated from the other rare earths by solvent extraction of its nitrate with methyl iso-butyl ketone; both groups are determined gravimetrically. Thorium is eluted from the ion-exchange resin with 3.6 N sulphuric acid and determined spectrophotometrically with thorin.The sulphuric acid-insoluble minerals are brought into solution by a double fusion method, and the determinations are carried out by a combination of ion-exchange and photometric procedures. Silica, phosphorus pentoxide, tin and chromium are determined by photometric methods, using separate portions of the sample.Lanthanum, yttrium and ytterbium are determined in a 1 M perchloric acid solution of the mixed rare earth oxides (less cerium) using flame photometry. Samarium, praseodymium and neodymium are determined by spectrophotometry.     

Elemental analysis in solutions by radioisotope excited X-ray fluorescence

The problem of spectrochemical analysis of elements in solutions has been investigated for a number of elements across the periodic table using radioisotope-induced energy dispersive X-ray fluorescence method. In this study a low intensity¹⁰⁹Cd X-ray source was used for characteristic X-ray excitation. Experimental parameters such as saturation thickness and critical thickness have been studied to evaluate their role in this method. Minimum detection limits, sensitivities and the nature of concentration calibration at critical thickness have been obtained as a function of Z to find the limits of the method. Results obtained have been discussed in the light of theories and potential areas of applicability of the method have been indicated.     

Precocentration method using an activatable yield tracer for neutron activation analysis

Previously, the use of an enriched stable isotope as an activatable yield tracer in preconcentration steps has been tested by use of commercially available enriched¹¹⁶Cd and¹⁵⁶Dy for biological standard reference materials.^1,2 In the present work, this method has been further applied to the determination of lanthanoid contents in various kinds of samples: one coal fly-ash, three Japanese standard rocks, and eight standard soils. Samples were decomposed by alkali fusion in the preconcentration step. Thirteen elements were determined for coal fly-ash and soil samples, and 14 elements for rocks. The data obtained for coal fly-ash and standard rocks are compared with the data reported in literature. The data for soil samples have been newly determined in the present work. The ordinary instrumental neutron activation analysis and radiochemical neutron activation analysis were also performed to confirm the accuracy and usefulness of the present method.     

Determination of 22 elements in geological samples by instrumental neutron activation analysis

An instrumental neutron activation analysis (INAA) method has been developed for multi-element determination in geological samples. The INAA method consists of irradiation of samples for 90 sec at a flux of 1.0·10¹² n·cm⁻²·sec⁻¹ and determination of 12 elements by using their short-lived nuclides. Samples have been re-irradiated for 3 hrs for measuring concentrations of another 10 elements. Precision and accuracy of the INAA method have been evaluated by analysing samples and USGS standard reference materials. Precision and accuracy are within±15% and ±10%, respectively.     

Qualitative soil mineral analysis by EDXRF,XRD and AAS probes

Soil minerals study is vital in terms of investigating the major soil forming compounds and to find out the fate of minor and trace elements, essential for the soil–plant interaction purpose. X-ray diffraction (XRD) has been a popular technique to search out the phases for different types of samples. For the soil samples, however, employing XRD is not so straightforward due to many practical problems. In the current approach, principal component analysis (PCA) has been used to have an idea of the minerals present, in qualitative manner, in the soil under study. PCA was used on the elemental concentrations data of 17 elements, determined by the energy dispersive X-ray fluorescence (EDXRF) technique. XRD analysis of soil samples has been done also to identify the minerals of major elements. Some prior treatments, like removal of silica by polytetrafluoroethylene (PTFE) slurry and grinding with alcohol, were given to samples to overcome the peak overlapping problems and to attain fine particle size which is important to minimize micro-absorption corrections, to give reproducible peak intensities and to minimize preferred orientation. A 2θ step of 0.05°/min and a longer dwell time than normal were used to reduce interferences from background noise and to increase the counting statistics. Finally, the sequential extraction procedure for metal speciation study has been applied on soil samples. Atomic absorption spectroscopy (AAS) was used to find the concentrations of metal fractions bound to various forms. Applying all the three probes, the minerals in the soils can be studied and identified, successfully.     

Non-destructive multi-element photonactivation analysis of environmental materials

A non-destructive method of photon-activation analysis with 30-MeV bremsstrahlung followed by high-resolution gamma-spectrometry has been developed for multi-element determination in ambient air and in air-pollution emissions. The sample materials were the NBS standard reference material. Fly Ash. and atmospheric particulates collected on a Millipore filter. Simultaneous irradiation of the sample with synthetic multi-element standards containing 33 elements has shown that the technique can determine up to 21 elements in a single sample. The method is simple and gives reproducible results.     

Determination of impurities in nuclear fuel element components by neutron activation analysis

Neutron activation analysis methods for the determination of impurities in zirconium cladding material and uranium oxide are described. Detection limits for the elements Al, Cd, Cr, Co, Cu, Hf, Fe, Mn, Ni, W and U in zirconium are below that required by the ASTM B 352-79 standard. The method has been tested on the NIST SRM 360a Zircaloy-2 from which the elements Na, Mg, Al, Ca, V, Cr, Fe, Co, Ni, Cu, Eu and U have been detected. The values for Cr, Fe, Ni and Cu are compared with the certified values. A method for the pre-irradiation separation of the elements Mg, Na, Al, K, Sc, Ca, V, Mn, Cr, Fe, Co, Cu, Zn, Rb, Zr, Cd, Cs, REE and Hf from uranium has been developed. A neutron activation analysis method for the determination of those elements in uranium is described. The method is tested by the analysis of the IAEA reference sample SR-54/64. The elements Al, Mn, V, Cu, Cr, Co, Ni and Fe have been detected and the results compared with the certified values.     

Counter-current chromatography for oil analysis: Retention features and kinetic effects

Application of counter-current chromatography (CCC) for oil analysis has been suggested for the first time. CCC looks very promising as a tool for pre-concentration and isolation of trace elements from oil. Features of stationary phase retention of two-phase liquid systems (oil or oil products–aqueous nitric acid solutions) in CCC have been investigated. The influence of physicochemical properties of crude oil and oil products used as a mobile phase on the volume of stationary phase (acidic aqueous solutions) retained in CCC was studied. Chromatographic behavior of several oil samples was studied. It has been shown that physicochemical properties of test oil influence its chromatographic behavior. Optimal values of density and viscosity (ρ < 0.85 g/cm³, n < 7 cSt) of crude oil and oil products that could be analyzed using CCC were estimated. The influence of the column rotational speed and flow rate of mobile phase on the stationary phase retention was also investigated. It is known that kinetic aspects (mass transfer of elements between phases) can play a very important role in selecting an optimal composition of stationary phase for the pre-concentration of elements from oil. The influence of nitric acid concentration in the stationary phase on mass transfer was studied. Kinetic characteristic for trace element recovery has been investigated for the optimization of pre-concentration conditions of trace elements from crude oil and oil products. The extraction recoveries of Zn, Mn, Fe, Ni, V, Cu, Cd, Pb and Ba by CCC in dynamic mode are in the range of 75–95% while they are lower than 35% under batch conditions.     

Computational analysis of atpB gene promoter from different Pakistani apple varieties

Apple is the fourth most important fruit crop grown in temperate areas of the world belongs to the family Rosaceae. In the present study, the promoter (∼1000 bp) region of atpB gene was used to evaluate the genetic diversity and phylogeny of six local apple varieties. atpB gene is one of the large chloroplastic region which encodes β-subunit of ATP synthase and previously it had been used largely in phylogenetic studies. During the present study, atpB promoter was amplified, sequenced and analyzed using various bioinformatics tools including Place Signal Scan, MEGA6 and BLASTn. During the phylogenetic analysis, obtained phylogram divided the studied varieties into two clusters revealing the monophyletic origin of studied apple varieties. Pairwise distance revealed moderate genetic diversity that ranges from 0.047–0.170 with an average of 0.101. While identifying different cis-acting elements present in the atpB promoter region, results exhibited the occurrence of 56 common and 20 unique cis-regulatory elements among studied varieties. The identified cis-acting regulatory elements were mapped as well. It was observed that Kala Kulu has the highest unique features with reference to the availability of cis-acting elements. Moreover, the possible functions of all regulatory elements present on the promoter sequence of atpB gene were predicted based on already reported information regarding their in vivo role.     

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