INAA and flame AAS of various vegetable reference materials

Summary INAA and flame AAS have been used for the analysis of a large number of vegetable reference materials. Out of all determined elements (28 by INAA and 11 by AAS) nine are common for both methods (Ca, Cd, Co, Cu, Fe, Mg, Mn, Na, Zn) and for these the possibilities of the two methods have been compared.     

Determination of trace elements in food by neutron activation analysis

Neutron activation analysis (NAA) methods have been developed for the determination of major, minor and trace elements in duplicate diets and individual food items. These include a cyclic instrumental NAA (CINAA) method for measuring Se content through its short-lived nuclide^77mSe; epithermal INAA (EINAA) for I and As; conventional INAA for Br, Ca, Cl, Co, Cr, Fe, K, Mg, Mn, Na, Rb, Sb, Sc, Sn and Zn; combination of EINAA and INAA for Al; radiochemical NAA (RNAA) for As, Au, Co, Cu, Fe, Hg, Mo, Sb, Se and Zn; and preconcentration NAA (PNAA) for U and Th. Accuracy of measurements have been evaluated by analyzing a number of biological and diet reference materials. Multielement concentrations of diets and foods have been measured by these methods.     

Determination of protein-bound trace elements in bovine kidneys

Concentrations of up to 16 elements have been determined in subcellular fractions of bovine kidney using INAA methods. Levels of Rb and Se have been measured by a cyclic INAA method. A conventional INAA method consisting of 2 irradiations and 3 counting periods has been employed to determine the other elements. Accuracy of measurements has been evaluated by analyzing several standard reference materials. Trace element content of reagents used has been investigated in detail. Fresh samples of bovine kidney have been homogenized in a buffer containing sucrose and HEPES, and the homogeneate separated into nuclei, mitochondrial, lysosomal, microsomal and cytosol fractions by successive differential centrifugation. Concentrations of trace elements have been measured in these fractions using the INAA methods.     

A comparison of INAA and ICP-MS/ICP-AES methods for the analysis of meteorite samples

Instrumental neutron activation analysis (INAA), inductively coupled plasma atomic emission spectrometry (ICP-AES) and ICP mass spectrometry (ICP-MS) (hereafter, ICPs) were applied to meteorite samples for the determination of elemental content. The analytical applicability and suitability of the three methods have been compared. Those comparisons led to the refinement of our analytical procedures for INAA and ICPs, yielding more reliable data. Our INAA data proved to be reliable enough for classifying meteorites, while the ICPs, especially ICP-MS, can characterize elemental abundance features in detail, as demonstrated by REE abundance patterns for the Allende meteorite. In this manner, INAA and ICPs can be used in a complementary fashion in cosmochemical studies.     

Optimal use of instrumental neutron and photon activation analyses for multielement determinations in sewage sludges

A combination of instrumental neutron activation analysis (INAA) and instrumental photon activation analysis (IPAA) methods has been developed for multielement determinations in a variety of sludges and fertilizers. The precision and accuracy of both the methods have been evaluated by analyzing replicate samples, NBS standard reference materials, and an interlaboratory intercomparison sewage sludge sample. The concentration rages of up to 50 elements in raw and chemical sludges, sludge-based fertilizers, and other organic and inorganic fertilizers are reported here. The advantages and limitations of the INAA and IPAA methods are also discussed here.     

Metrology for Chemical Measurements and the Position of INAA

Metrology systems are being established by various countries for the worldwide comparability of data related to trade, industrial products, health, and the environment. This has in turn led to an increased interest in methods that have the highest possible accuracy and precision. The relevance of instrumental neutron activation analysis (INAA) for metrological science has been evaluated. It is concluded that INAA is a suitable technique for method validation, proficiency testing, development of reference materials and reference methods. Moreover, it is concluded that INAA may comply with the CCQM definition of a definitive or primary ratio method provided that the uncertainty in the results is reduced to much lower levels compared to those currently encountered in most NAA laboratories.     

Analytical methods for the environmental quantification of uranium isotopes: Method of validation and environmental application

The use of depleted uranium in military ordinance has led to an increasing need to determine isotope-specific uranium concentrations in environmental matrices. To this end, gamma-ray spectrometry, ICP-MS and INAA methods have been validated, in accordance with the ISO 17025 standard. Reporting limits of 0.21 (U-235) and 0.91 (U-238) ng/L were obtained by ICP-MS analysis of water. Higher reporting limits were obtained for INAA (U-238 only) validations of water and gamma-ray spectrometric validations of soil and water. Accredited methods have been used to determine uranium concentration and isotope ratio of samples obtained from the Defence Research and Development Canada Valcartier, Quebec.     

Activation analysis study on subcellular distribution of trace elements in human brain tumor

The concentrations of up to 11 elements in subcellular fractions of human brain (normal and malignant tumor) have been determined by a combination of gradient centrifugation and INAA methods. Samples of human brain were homogenized in a glass homogenizer tube, the homogenate was separated into nuclei, mitochondrial, myelin, synaptosome fractions, and these fractions were then analyzed using the INAA method. The discussions of elemental subcellular distributions in human brain malignant tumor are presented in this paper.     

Sensitivity improvements in the determination of mercury in biological tissues by neutron activation analysis

The possible association of dental amalgam surface exposure, brain mercury (Hg) levels, and pathological markers of Alzheimer's disease (AD) in the brain is the subject of an on-going study in our laboratory. Two radiochemical neutron activation analysis methods and the use of instrumental neutron activation analysis (INAA) with Compton suppression spectrometry have been evaluated for improving our INAA Hg detection limit (2.8±0.6 ng/g, wet-weight basis) in human tissue. Large numbers of samples dictated the use of a purely instrumental method or rapid, simple radiochemical separations. Human brain tissues and NIST biological standards were analyzed using a precipitation of Hg₂Cl₂, a solvent extraction utilizing sodium diethyldithiocarbomate, conventional INAA, and INAA with Compton suppression. The radiochemical precipitation of Hg₂Cl₂ proved to be the most useful method for use in our study because it provided a simultaneous, quantitative determination of silver (Ag) and a Hg detection limit in brain tissue of 1.6±0.1 ng/g (wet-weight basis).     

Determination of Heavy Metals as Environmental Pollutants: Use of Instrumental Neutron Activation Analysis

The simultaneous determination of heavy metals by instrumental neutron activation analysis (INAA) in some environmental samples have been considered. A new approach has been proposed to assess the potentialities and the most adequate use of INAA for each particular heavy metal.     

Instrumental neutron activation analysis based on k0-standardization method as compared with other methods in the analysis of the IAEA inter-comparison test

Results of inter-comparison test organized by the IAEA are analyzed according to the contribution and performance of INAA as non-destructive method for trace elements analysis as compared to other techniques. Several methods were employed for certifying the biological sample (IAEA-0140) and were also compared. It is shown that NAA is the method of a good accuracy and precision. The biological sample has been investigated by INAA based on semi-absolute technique. More than 30 elements have determined without using standards. The reference materials, which are certified in this manner and utilized as primary standard, are also discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characterization of simulated vitrified highly active waste and its leachates by neutron activation

Neutron activation analysis (NAA) methods have been developed for the simultaneous determinations of multielement concentrations in various types of glass and their leachates. The epithermal instrumental NAA (EINAA) method involves the irradiation of samples in a Cd-shielded site for 2–5 min in order to determine levels of of up to 13 elements through their short-lived nuclides. Another 15 elements can be measured via their long-lived nuclides using conventional instrumental NAA (INAA). Accuracy of the methods have been evaluated by analyzing certified reference materials. The limits of detection for all elements are reported. The methods have been applied to sodium borosilicate and sodium calcium aluminosilicate glass samples in order evaluate their suitability as a host matrix for immobilizing high level radioactive waste.     

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.     

Analytical procedure for the determination of thorium, zinc and potassium in diet samples

Instrumental neutron activation analysis (INAA), and atomic absorption spectrometry (AAS) have been used for the determination of trace amounts of thorium, zinc, and potassium in diet samples. Interlaboratory comparison has been made. The z-scores show that INAA can be used to determine thorium and zinc whereas AAS can be employed to determine potassium in diet samples.     

Composition and morphology of stack emissions from coal and oil fuelled boilers

Instrumental neutron activation analysis (INAA) together with scanning electron microscopy (SEM) have been used in the study of fly ash from large electric power and heating plants. Two basic kinds of fly ash originating either from brown coal or heavy-oil combustion can be characterized both by morphology and trace element composition. INAA technique used consisted of both short (1 min) and long (2 h) activations to ensure the determination of 30–40 elements in each fly ash sample. The average composition and determination limits obtained by INAA for coal fly ash produced in several electric power plants burning two kinds of brown coal have been compared with those obtained for fly ash originating from heating plants burning heavy-oil. Coal fly ash showed much higher concentrations of many elements especially of Sc. La, Th, Cs, Ce, Sm, Rb and Al in comparison with oil fly ash. On the other hand, the latter contained relatively high concentrations of V and Ni. The results of INAA of fly ash samples can be used for the projection of efficient separating devices and for the evaluation and prediction of contamination levels in the vicinity of large emission sources.     

Comparison of instrumental neutron activation analysis of geological materials with other multielement techniques

Results obtained for 12 elements in approximately 1600 rocks by instrumental neutron activation analysis (INAA) are compared with those obtained by ICP emission spectrometry (ICP-ES), XRF, and atomic-absorption spectrometry (AAS). Sample duplicates and two controls are used to evaluate the precison of the methods investigated. Application of a method (Maximum Likelihood Functional Relationship) to determine and quantify rotational and translational bias is demonstrated. The elements Na, Fe, Ba, Co, Cr, La, Ni and Rb can be determined in rocks by INAA with sufficient sensitivity and precision, whereas the determination of Ag, Yb, Zn and Zr suffers from inadequate sensitivity. Good agreement is seen in the results for Na (by INAA, ICP-ES and XRF) and AG (INAA and AAS). A significant positive bias (13% or less) is evident in the comparison of results by INAA and ICP-ES or XRF for Cr, Ba, Ni and Fe over a wide range of concentration. A similar trend, though less significant, is observed for the elements Yb, Rb, La and Co; the upper limit of concentration for satisfactory determination is within a decade of the highest detection limit for these elements. Rotational and translational bias is evident for Zn in the comparison of data obtained by INAA and ICP-ES, the results by INAA being appreciably lower above about 400 ppm Zn.     

Determination of trace and toxic elements in Korean rice CRM by INAA, ICP and AAS

Trace and toxic elements in Certified Reference Material (CRM) made of Korean rice at the Korea Research Institute of Standards and Science have been analyzed by Instrumental Neutron Activation Analysis (INAA). Data intercomparison from the measurement with those of Atomic Absorption Spectrometry (AAS) and Induced Coupled Plasma Spectrometry (ICPS) has been studied. The powdered samples were sterilized at 1.5·10⁶ rad in the bottles using a⁶⁰Co source after sieving and spiking to specific elements such as As, Cd, Cr, Cu and Hg and then the homogeneity of samples was assessed. Rice flour (SRM 1568a) and standard solutions made by the National Institute of Standards Technology (NIST) were used to construct the calibration curves for the INAA and the chemical methods, respectively. The uncertainties and concentration of constituent elements were determined and the possibility of their use for analytical quality control was considered.     

A contribution to the certification of some elements in eight vegetal reference materials by using instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) has been applied to the determination of 21 elements in 8 different vegetal samples, to be used as reference materials in 35 European laboratories (CII). Many of these elements hitherto have not been evaluated; they can be useful markers in many environmental problems. The INAA values are compared with CII non-nuclear analytical techniques results. Some rare earths elements (REE) have been also determined and their chondritic ratio versus atomic radius is reported.     

QA/QC Procedures,Validation Method,Traceability and Intercomparisons

Summary This work provides a systematic experimental approach to the demonstration of viability of instrumental neutron activation analysis (INAA) in chemical metrology. The practical approach was derived from a complete survey of uncertainty components that affect the INAA measurement process. These uncertainty components were classified by their magnitude and origin and subsequently minimized by appropriate steps in the INAA process. The process was tested with the INAA determination of Cr in SRM 1152A stainless steel; the Cr value is certified at 17.76% with an estimated uncertainty of 0.04% (0.23% relative). The INAA results from this procedure are in agreement with these specifications. Similar procedures have been applied to INAA multi-element determinations in a high temperature alloy. Agreement with available consensus values was demonstrated in the alloy. The guidelines on the determination of uncertainty were fully met, providing through INAA a valuable independent non-destructive tool in chemical measurements of metrological value such as required in the CCQM key comparisons.     

Speciation and instrumental neutron activation analysis for arsenic in water samples

Ground water samples obtained from West Bengal, India were analyzed for total arsenic and its inorganic species contents by instrumental neutron activation analysis (INAA). Two anion exchange separation methods using Dowex 1X8 in chloride and acetate forms were standardized for the speciation of As(III) and As(V) using radiotracers. The method by Dowex 1X8 in the acetate form was validated using synthetic mixtures of As(III) and As(V), and applied to water samples; the species concentrations were determined by INAA. The accuracy of the INAA method was evaluated by analyzing the NRCC CRM DORM-2 for total arsenic.