Vanadium determination in rat tissues and biological reference materials by neutron activation analysis

Vanadium was determined in adrenal gland, brain, ileum, kidney, liver, lung, muscle, myocard, skin, spleen, gonads, thyroid, and tibia of rats fed with normal diet and exposed to high vanadium doses in drinking water. Both radiochemical neutron activation analysis (RNAA) and instrumental neutron activation analysis (INAA) were employed. The RNAA procedure consisted in dry ashing samples prior to irradiation and vanadium separation from the irradiated samples by extraction with N-benzoyl-N-phenylhydroxylamine (BPHA) in toluene from 5 mol·l^–1 HCl. Vanadium accumulation as a function of a type of the tissue, exposure time, sex of rats, and administration of V(IV) or V(V) was studied. For quality assurance purposes, the biological (standard) reference materials NBS SRM 1571 Orchard Leaves, NBS SRM 1577a Bovine Liver, IAEA H-4 Animal muscle, and Bowen's Kale were analyzed.Presented at the 2nd Balkan Conference on Activation Analysis and Nuclear-Related Analytical Techniques, Bled, 4–6 October, 1989.     

Distribution patterns of rare-earth elements in biological materials evaluated by radiochemical neutron activation analysis

This study deals with the quantitative determination of eight REE's viz, La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu as an Integral part of a post-irradiation chemical separation scheme for the determination of 14 trace elements in biological materials. REE values are given for NBS Orchard Leaves SRM 1571, NBS Bovine Liver SRM 1577 and Bowen's Kale, as well as for some other biological (reference) materials of plant, animal and human origin. Chondritic-normalized REE patterns of these materials are discussed. It is shown that differentiations in REE-pattern between soil and plant may occur, and also that within the human body different modes of fractionation of REE's take place.     

Elemental characterisation through instrumental neutron activation

Neutron activation has been used to characterise the elemental composition of geological and biological materials. Both reactor neutrons and 14 MeV neutrons have been used. Instrumental approach has been followed incorporating coincidence measurements. The system and the methodology have been discussed. The results for the 3 Canadian rock standards (SY-2, SY-3, MRG-1), a trachyte, 2 NBS SRMS (1571 Orchard leaves, 1577 Bovine liver) and an IAEA intercomparison sample, Animal Muscle H.4 have been given for 15–25 elements.     

Characterisation of biological RMs for potential use in human brain analysis

Summary In order to investigate the precision and accuracy obtainable with instrumental neutron activation analysis (INAA) and inductively coupled plasma atomic emission spectrometry (ICP-AES), five different biological reference materials were analyzed. Four of them originated from the US National Institute of Standards and Technology (NIST) (Bovine Liver (SRM 1577; 1577/a; 185/A), Orchard Leaves (SRM 1571)) and one of them came from the International Atomic Energy Agency (IAEA) (Animal muscle (H-4)). The decomposition efficiency of microwave acid digestion was examined in comparison to digestions carried out in a Parrbomb. Five to ten subsamples of each material were subjected to the two digestion procedures and the solutions were analyzed by ICP-AES. The dried samples were analyzed by INAA. Up to 16 elements (Al, B, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Zn) were determined in various materials.     

Rare earth element patterns in biotite muscovite and tourmaline minerals

Rare earth element concentrations in the minerals biotite and muscovite from the mica schist country rocks of the Etta pegmatite and tourmalines from the Bob Ingersoll pegmatite have been measured by INAA and CNAA. The concentrations range from 10^–4 g/g to 10^–10 g/g. The REE patterns of biotite, muscovite and tourmaline reported herein are highly fractionated from light to heavy REE. The REE concentrations in biotite and muscovite are high and indigenous. The pegmatite tourmalines contain low concentrations of REE. Variations in tourmaline REE patterns reflect the geochemical evolution of pegmatite melt/fluid system during crystallization.Work supported by the U. S. Department of Energy under Contract DE-AC06-76RLO 1830.     

The determination of zirconium in biological materials by photon activation analysis

Non-destructive photon activation analysis with 30-MeV bremsstrahlung has been applied for the determination of zirconium in biological materials. The materials investigated were the NBS SRMs Orchard Leaves and Bovine Liver, and various tissues of rats. The detection limits of this method for a 2 h irradiation are 0.1 g for Orchard Leaves, 0.04 g for Bovine Liver and animal tissues. The zirconium contents of animal tissues obtained in this work appear to be significantly lower than the values reported earlier. New data on zirconium in the NBS SRMs are presented.     

Distribution of thorium in human tissues

Neutron activation followed by simple radiochemical separation was employed to determine the concentration of thorium (²³²Th) in different human tissues. The median²³²Th concentrations (ng/g) in tissues with ranges given in parentheses are lymph nodes: 64.7 (31.4–85.5), lungs: 9.2 (1.5–16.0), hair: 5.2 (2.9–11.0), kidney: 1.7 (0.9–4.0), liver: 0.9 (0.2–4.9) and blood 0.01 (0.006–0.030). The reliability of analysis was tested by analyzing standard reference material Orchard Leaves (US, NBS).     

Evaluation of homogeneity of selected reference materials for selenium by cyclic neutron activation analysis

The homogeneity of four reference materials was evaluated for Se by cyclic instrumental neutron activation analysis (CINAA). The relative standard deviation for Se measurements at ppb levels by CINAA was <12% for NIST Wheat Flour (SRM 1567) in 5–10 mg samples, while it was <11% for Chinese Hair (HH–CH-1), <13% for IAEA Animal Muscle (H-4) and 25% for IAEA Animal Blood (A-13) in 50 mg samples. The highest relative subsampling uncertainties were observed in the mass range of samples 50 mg for Chinese Hair, 100 mg for Wheat Flour and Animal Muscle and 300 mg for Animal Blood. The results of a one-way analysis of variance indicate that all reference materials above these mass ranges are adequately homogeneous with respect to Se distribution. Our data suggest that these materials, except Animal Blood, can be used as reference standards for Se in Quality assurance programs well below the sample masses re commended by the issuing agencies.     

A highly selective diethyldithiocarbamate extraction system in activation analysis of copper,indium, manganese and zinc

A versatile separation system based on the extraction of dithiocarbamates and applicable to the determination of copper, managanese, zinc and indium in a wide selection of materials by activation analysis is described. After the dissolution of the sample and a few simple operations which eliminate specific interferences, depending upon the material (e. g. sodium and gold in the NBS Standard Reference Glasses), carbamates are extracted under specific conditions by addition of appropriate complexing agents and selective stripping. Extreme separation factors permit interference-free counting using a sodium iodide detector. For example, indium is separated from a hundred thousand fold excess of manganese in the determination of the two elements in Orchard Leaves. Results are also presented for all four elements in Bowen's Kale, NBS Bovine Liver, and for Cu, In and Mn in the 0.02 ppm and 1 ppm SRM glasses.     

Neutronenaktivierungsanalytische Bestimmung des Chromgehaltes von Laboratoriumskaninchen-Skelettmuskel

Zusammenfassung Als Beitrag zur Ermittlung der richtigen Werte der Chromgehalte von menschlichen und tierischen Geweben und Körperflüssigkeiten wurde der Chromgehalt von Laboratoriumskaninchen-Skelettmuskel neutronenaktivierungsanalytisch bestimmt. Bisherige Angaben anderer Autoren: <7,1–121 ng/g. Die Verbesserung einer in der Literatur angegebenen ⁵¹Cr-Abtrennung durch Chromylchloriddestillation und die erforderlichen Maßnahmen zur Minimierung des Chromblindwertes werden beschrieben. Dessen Hauptanteil wird durch die Restverunreinigung der Bestrahlungsampullen-Oberfläche mit Chrom bedingt und beträgt 0,049 ng Cr (ohne Gefriertrocknung) bzw. 0.12 ng Cr (mit Gefriertrocknung). Analysen von Standardreferenzmaterialien (SRM) ergaben Chromgehaltswerte, die bei NBS-Citrus Leaves mit dem Zertifikatswert, bei IAEA animal muscle (H-4) mit dem neuesten Literaturwert von 9,2±2,5 ng/g übereinstimmen. Im Falle von NBS-Orchard Leaves erwies sich, daß dieses SRM für die Überprüfung der Methode ungeeignet ist. In Analysen von Oberschenkelmuskel-Proben von Bastardkaninchen resultierten Chromgehalte von 6,2–22,9 ng/g (bezogen auf Frischgewicht). Aus dem Vergleich dieser Daten mit dem früher gefundenen Wert von 1,2 ng/g, dem Literaturwert <7,1 ng/g und dem auf Frischgewicht berechneten H-4-Wert von 2,5 ng/g folgt, daß die Chromgehalte von Säugetier-Skelettmuskel innerhalb eines breiten Bereiches liegen dürften, auch die von Muskel einer Subspecies.

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Determination of the chromium content of laboratory rabbit skeletal muscles by neutron activation analysis

Summary The accurate values of the chromium contents of human and mammalian tissues and body fluids and appropriate procedures for their determination are still a matter of discussion. In this connexion, the chromium content of skeletal muscle of laboratory rabbits has been determined using neutron activation analysis. Data hitherto published by other authors: <7.1–121 ng/g. The procedure for separation of ⁵¹Cr by distillation of chromium oxychloride, described in the literature, has been improved. The arrangements necessary to minimize the chromium blank values are described. The main component of this blank is caused by the residual chromium contamination of the surface of the sample vial; typical values of this component are 0.049 ng Cr (without lyophilization) and 0.12 ng Cr (with lyophilization). The analyses of standard reference materials (SRM) yielded values of the chromium contents that are in agreement (i) with the certified value in the case of NBS Citrus Leaves, and (ii) with the latest published value of 9.2±2.5 ng/g in the case of IAEA animals muscle (H-4). NBS Orchard Leaves was found not to be an appropriate SRM for testing the method. In analyses of samples of thigh muscle of bastard rabbits chromium contents of 6.2–22.9 ng/g (fresh weight basis) were obtained. Comparison of these data with a previously found value of 1.2 ng/g, the literature value <7.1 ng/g and the value 2.5 ng/g for H-4 calculated on fresh weight basis indicated that the chromium contents of mammalian skeletal muscle might lie in a broad range, even for a subspecies.

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Herrn Prof. Dr. K. H. Lieser zum 65. Geburtstag gewidmet     

Determination of selenium(IV) by anodic stripping voltammetry with an in situ gold-plated rotating glassy carbon disk electrode

The application of an in situ gold-plated glassy carbon disk electrode to the determination of selenium(IV) by anodic stripping voltammetry is described. A single anodic stripping peak is obtained for solutions containing less than 1 × 10^-6 M Se(IV). The minimum concentration detected was 2 × 10^-9 M Se(IV). The determination of selenium in NBS SRM 1577 (Bovine Liver) by anodic stripping voltammetry with an in situ goldplated rotating glassy carbon electrode yielded a value of 1.14 ± 0.07 μg Se g^-1 compared with a certificate value of 1.1 ± 0.1 μg Se g^-1.     

In-situ micro-analysis of platinum and rare earths in ferromanganese crusts by laser ablation-ICP-MS (LAICPMS)

A 500 mJ Nd: YAG laser coupled to an inductively coupled plasma mass spectrometer (ICPMS) has been used for the direct determination of platinum (Pt) and the rare earth elements (REE) in concentration micro-profiles through ferromanganese crusts from the South Pacific. The instrument has been calibrated with briquetted powder pellets of U.S.G.S. reference materials NOD-A-1 and NOD-P-1. Linear calibration curves including the origin have been obtained for all elements of interest. An external calibration strategy has been developed which also accounted for variations in instrument response. The precision of the LA-ICP-MS measurements in this matrix has been 4–5% for platinum and <4% for the rare earths. Platinum concentrations have varied from 150 ng g^–1 to 500 ng g^–1 through the analysed microprofile. Two major peak areas in the platinum concentration profile have correlated roughly with cerium values and with changes in the normalised REE pattern: an enrichment of Pt coincides with a pronounced positive cerium anomaly and with an enrichment of the heavy REE relative to the light REE.     

Determination of rare earth elements in geological samples by inductively-coupled plasma atomic emission spectrometry after oxalate coprecipitation and cation-exchange column separation

A method for separation and determination of traces of 14 rare earth elements (REEs) in geological samples is described. Determination by inductively-coupled plasma atomic emission spectrometry follows oxalate coprecipitation of the REEs with calcium as carrier and cation- exchange column separation in nitric acid. The combination of the two separation techniques improved the low recoveries found for Sm, Eu, and Gd when only ion-exchange was used, especially for iron- and aluminum-rich samples. The method was applied to the analysis of geological standard materials NBS SRM 688 (basalt), NBS SRM 278 (obsidian), GSJ JB-1 (basalt), GSJ JA- 2 (andesite), and CCRMP SY-3 (syenite). The results were evaluated on the basis of chondrite- normalized rare earth element distribution patterns.     

A Simplified Method for Determining Arsenic and Antimony by the Hydride Evolution-Atomic Absorption Method

Abstract

A plastic disposable syringe hydride generator and aspirator system coupled with atomic absorption spectroscopy is shown to give results comparable to complex systems costing many times more. Details of operation, sensitivity, range of linearity and detection limits are outlined. Analyses performed on National Bureau of Standards Orchard Leaves and Bovine Liver are given and the results compared with NBS provisional values.     

A method to investigate the interaction of rare earth elements in aqueous solution with metal oxides

A method is described which can be used to investigate the interaction of dissolved metals with particulate material. Low level concentrations (10^–9M) of rare earth radiotracers were used to investigate their sorption onto synthetic mineral oxide surfaces. The preparation of rare earth radiotracers by neutron activation is discussed in detail. A kinetic approach was employed to investigate the interaction of dissolved metals and suspended mineral oxides. Amorphous iron oxyhyroxide, a phase commonly found in nature, was used in sorption experiments carried out in seawater at pH 7.8 and 2°C. Results of this study indicate a high affinity of the rare earth elements (REE) for the iron oxide surface (evidenced by fast uptake and high partition coefficients) and reveal a fraction between light and heavy REE.     

Usefulness of thermal and epithermal cyclic activation analysis with a reactor system

A new cyclic activation system (CAS) has recently been installed at the University of London Reactor and is briefly described. It has the unique feature that it allows choice as to whether irradiations are to be carried out under cadmium or in a bare tube and thus both epithermal and thermal cyclic activation analysis can be performed. Measurements in this work, have been carried out using a Ge(Li) detector but the facility allows other detectors to be used and an additional return line from the central distributive mechanism of the system (not yet installed) will allow samples to be cycled to and from a neutron detector thus providing the possibility of measuring radionuclides emitting delayed neutrons. By way of illustration of the theory of cyclic activation analysis, since the paper is to serve as an introduction to other papers in the conference using the technique, the results of a calculation for the detection of uranium under thermal and epithermal conditions are presented and compared to conventional activation. The usefulness of cyclic neutron activation analysis (CNAA) is also demonstrated in cases where identification of an isotope through its gamma-ray energy alone is not sufficient and conformation is achieved through determination of the half-life of the activity of interest, without resort to further experimental work or additional instrumentation. This leads on the thorny problem as to whether Poisson statistics should continue to be used in cases where the period of observation is of the same order as the decay constant of the activity of interest and it is pointed out how CNAA can be employed to extract the information required if a binomial-type statistical density function is used. Finally in order to prove the system and the cyclic method and as a preliminary to a larger project, prepared single element standards and standard reference materials [NBS Orchard Leaves, NBS Bovine Liver, IAEA Animal Blood, IAEA Hair standard and Bowen's Kale] are analysed under the two cyclic irradiation conditions. Sensitivities and cadmium ratios are obtained for the twelve elements from the elemental standards (Na, Al, Sc, Ge, Se, Rh, Pd, Ag, Ce, Er, Hf and Pb) and detection limits for a number of elements of interest presented for the standard reference materials.     

Study of the correlation of trace elments in human hair and internal organs by NAA

24 male autopsy cases aged 35–60 years have been collected from Shanghai China to study the relationships between human hair and internal tissues. Autopsy samples of hair, kidney-cortex, liver and lung were analyzed. A radiochemical neutron activation analysis (RNAA) based on a simple group extraction scheme was used for measuring the trace elements As, Cd, Hg, Cu and Zn. Zinc diethyldithiocarbamate Zn(DDC)₂ and methly isobutyl ketone-iodide have been chosen as reagent. Trace element of Se was determined by instrumental neutron activation analysis (INAA). A SLOWPOKE reactor with a thermal neutron flux of 8·10¹¹ n·cm^–2·s^–1 and a swimming pool type reactor with a thermal neutron flux of 1·10¹³ n·cm^–2·s^–1 were used for short and long irradiation of samples, respectively. The reliability of methods has been checked by analyzing biological standard reference materials Horse Kidney (IAEA H8), Tomato Leaves (NBS 1573) and Human Hair (NIES-5). The analytical results show that toxic elements As, Cd and Hg exist in a larger individual variability than the essential elements of Cu, Se and Zn for each tissue. A linear regression analysis related to the six elements of primary interest for the IAEA Coordinated Research Program (CRP) has been done by a computer program for each pair of hair-tissue. A positive correlation is found between concentration of As in hair and kidney-cortex, the correlation coefficient r is 0.751 (p<0.01). Positive correlations between concentration of Se in hair and liver, kidney-cortex and lung are also observed in this study. It shows that the elements As and Se in hair may be useful indicators for assessing certain internal tissues of normal persons. A comparison of Cd concentration in lung shows a significant difference between smokers and non-smokers. A significant correlation between element Cd and Zn in kidney-cortex is also presented in this paper.     

Application of independent methods and standard materials: An effective approach to reliable trace and ultratrace analysis of metals and metalloids in environmental and biological matrices

Summary Reliable trace analysis is only possible, if during methodological development independent analytical procedures or working standards and Standard Reference Materials are applied. Since at present only a few appropriate Standard Reference Materials are available, the existing gap has to be filled with e.g. working standards. Besides the application of independent methods, also as laboratory intercomparisons, for the determination of Pb, Cd, Cu, Ni and Hg in natural waters, sea water, urine, whole blood, marine organisms and wine, the current use of the NBS Standard Reference Materials Bovine Liver and Orchard Leaves is described. Further data are given of long term storage studies with blood samples and results of trace metal determinations in two working standards, fish muscle homogenate and algae, and in tentative future Standard Reference Materials (dried whole blood, blood plasma, phytoplankton, human hair, two aquatic and a terrestrial plant material).

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Anwendung unabhängiger Methoden und Standardmaterialien: Ein Weg zur zuverlässigen Spuren- und Ultraspurenanalyse von Metallen und Metalloiden in Umwelt- und biologischen Matrices

Zusammenfassung Zuverlässige Spurenanalyse ist nur möglich, wenn während der methodischen Entwicklung entweder unabhängige Verfahren eingesetzt oder Arbeitsstandards, bzw. Standard-Referenz-Materialien verwendet werden. Da gegenwärtig nur einige wenige geeignete Standard-Referenz-Materialien verfügbar sind, muß die bestehende Lücke u.a. mit Arbeitsstandards geschlossen werden. Neben der Anwendung unabhängiger Methoden, auch als externer Methodenvergleich, zur Bestimmung von Pb, Cd, Cu, Ni und Hg in Süß- und Meerwasser, Harn, Vollblut, marinen Organismen und Weinen wird die laufende Anwendung der NBS Standard-Referenzmaterialien Bovine Liver und Orchard Leaves beschrieben. Weiter werden Daten von Langzeitstudien mit Blutproben sowie die Ergebnisse der Bestimmungen von Spurenmetallgehalten in den Arbeitsstandards Fischmuskel-homogenat und Algen sowie in Entwicklung befindlichen Standard-Referenzmaterialien (Trockenvollblut, Blutplasma, Phytoplankton, menschliches Haar sowie zwei aquatischen und einer terrestrischen Pflanze) mitgeteilt.

Presented at Euroanalysis III conference, Dublin, August 20–25, 1978     

Rare earth elements determination and distribution patterns in surface marine sediments of the South China Sea by INAA,Malaysia

Results obtained from the analysis of sediments surface samples taken from rivers mouth and polluted marine environment were analyzed for REE contents to determine the concentrations of La, Ce, Sm, Eu, Tb, Dy, Lu and Yb using instrumental neutron activation analysis. Thirty surface samples were collected from ten sites in the coastal marine sediments of the South China Sea along 957 km stretch of the east coast of Peninsular Malaysia. The samples prepared in the powdered form before irradiating them in a neutron flux of ~4 × 10¹² n cm⁻² s⁻¹ at 750 kW power using the TRIGA Mark II research reactor at Malaysian Institute for Nuclear Technology (MINT). Results of the total concentration are used to establish baseline data in environmental pollution assessment and to develop the correlations between the Ce/Ce* anomalies and the distribution patterns of some the light rare earth elements (LREEs) and the heavy rare earth elements (HREEs). The Chondrite-normalized REE pattern from each site examined and used to explain the sedimentation patterns by anthropogenic activities and by natural processes such as shoreline erosion, weathering deposits. Shale-normalized (NASC) patterns suggest enrichment of LREEs relative to the HREEs with a positive Ce/Ce* anomaly. Validation of the used method was done using a Soil-7 SRM.     

Evaluation of the solid sampling technique for the determination of aluminium in biological materials by atomic absorption and atomic emission spectrometry

Summary Results for the determination of aluminium in several biological materials by atomic absorption and atomic emission spectrometry using the solid sampling technique in connection with a constant temperature furnace are given. A comparison was made with a dissolution procedure and good agreement was generally obtained. With the solid sampling technique it was possible to calibrate against aqueous standards and to achieve a precision of better than 10% r.s.d. for NBS 1577a Bovine Liver and IAEA H-4 Animal Muscle, providing that the sample mass was greater than 1.3 mg and that the peak area was evaluated. Laboratory air and the solid sampling procedure were identified as possible sources of contamination.

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Auswertung der Feststofftechnik für die Bestimmung von Aluminium in biologischen Materialien durch AAS und AES