Determination of gold in gold ores

The gold content of placer gold flakes and gold bearing ores has been determined by instrumental neutron activation analysis /INAA/ and radiochemical neutron activation analysis /RNAA/. It was discovered that significant errors result in the instrumental method for gold flakes as small as 10 mg due to sample self-absorption of neutrons during irradiation. Reliable results were obtained, for both ore samples and gold flakes, by dissolving the samples in aqua regia prior to irradiation.     

The determination of bromine in biological material by thermal neutron activation analysis

The determination of bromine in biological material by thermal neutron activation analysis using instrumental [Ge(Li)] and radiochemical separation techniques is described. The radiochemical method is ten times more sensitive (0.4 ng) than the instrumental technique but both may be used for analysis of the majority of human tissue samples. Both techniques are rapid, simple, accurate and may be used for batch analysis.     

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).     

Comparison of INAA and RNAA Methods with Thermal-Ionization Mass Spectrometry for Iridium Determinations in Atmospheric Tracer Studies

The sensitivity and precision of instrumental neutron activation analysis (NAA), radiochemical neutron activation analysis (RNAA), and thermal ionization mass spectrometry (TIMS) are compared for the determination of Ir in ambient size-fractionated aerosol particulate samples. The results of the TIMS analyses indicated high analytical precision (0.2% at >50 pg Ir), but the sensitivity of detection was limited by blank values (300–500 fg). The sensitivities for INAA and RNAA were comparable, i.e., 60 to 90 fg in size-segregated particulate samples.     

Thermal neutron irradiation induced defects in n-GaAs and their annihilation by annealing processes

Forperforming radiochemical photocorrosion measurements, n-GaAs samples were irradiated with thermal neutrons. The resulting changes in charge carrier concentration and mobility are determined by far IR reflectance measurements. A great part of the neutron irradiation induced defects could be annihilated by annealing at temperatures of up to 650°C. The neutron irradiation induced defects are responsible for essential changes in photoelectrochemical characteristics of n-GaAs electrodes in aqueous electrolytes. The photocurrent onset potential is shifted in positive direction and the maximum photocurrent is decreased. After annealing treatment the original photoelectrochemical behavior is restored.     

Method for determination of silicon in plant materials by neutron activation analysis

Silicon has been found to be an essential element for the growth and development of many ecomomically important plants such as sugarcane, rice, oats, and wheat. A method is described for the quantitative determination of silicon in plant samples. Measurements were made with two Ge(Li) detectors matched with a multiplexing unit to provide a single amplified signal to a computerized analyzer system. For those materials containing greater than 0.5 weight percent silicon, the reaction²⁹Si(n, p)²⁹Al (1273 keV) provides a direct measurement of the quantity of silicon provided the irradiation is done in a special boron nitride capsule to reduce interferences from thermal neutron reactions and a correction is made for the single escape line from²⁸Al (1268 keV). For lesser quantities of silicon, a technique which utilizes the fast neutron reaction²⁸Si(n, p)²⁸Al is preferred. Corrections for the interference produced by the presence of phosphorus³¹P(n, α)²⁸Al are made by determining the phosphorus content following the instrumental analysis using a unique application of neutron activation analysis, i. e., measurement of tungsten in tungstomolybdophosphoric acid produced when molybdate and tungstate ions are added to dissolved samples of the plant material containing phosphorus. Aluminum, which may also produce an interference by thermal neutron reaction²⁷Al(n, γ)²⁸Al, is determined directly from the original activation data after subtracting out the effect of the phosphorus. Thus, three irradiations in the pneumatic sample irradiator are necessary; one short irradiation (1 min) without thermal neutron shielding, a longer irradiation (6 min) in the boron capsule, and a final irradiation of the tungstomolybdophosphoric acid provide all data required to accurately determine silicon in plant materials. A computer program has been developed that provides rapid reduction of the data in final report format. Elements such as sodium, chlorine, calcium, manganese, potassium, and magnesium extrinsic to the analysis for silicon are also determined by this method. The method has been tested on a large number of samples and reliable results are obtained with less than 0.2 g of sample. This work was supported by Grant 533 from the Michigan Memorial—Phoenix Project.     

A radiochemical method for neutron activation analysis of arsenic in biological samples and its potential use in epidemiology studies

Epidemiology studies that examine As toxicity rely on the accurate measurement of As in biological matrices to determine exposure. Accurate measurement of As in biological matrices is challenging by instrumental NAA due to the production of high and variable activities of ²⁴Na, ¹²²Sb and ⁸²Br which contribute to increased background and difficulty quantifying the ⁷⁶As peak at 559 keV. This paper describes a novel radiochemical NAA method for As analysis in biological matrices. Samples were irradiated at the University of Missouri Research Reactor in a flux of 6.5E + 13 n/cm²/s. Following irradiation samples were transferred to polypropylene tubes with As carrier and digested using a combination of nitric acid and hydrogen peroxide. Arsenic was separated by absorption on magnetite nanocyrstals followed by vacuum filtration. Samples were counted using an automated sample changer and HPGe detector with a Canberra Lynx digital signal analyzer. The accuracy and precision of the RNAA results were evaluated by measuring As in NIST SRM 1575 Pine Needles, 1571 Orchard Leaves, 1566 Oyster Tissue, 1577 Bovine Liver, and NCS DC 73347 Hair. Arsenic was measured in duplicate nail samples by instrumental neutron activation analysis followed by radiochemical neutron activation analysis.     

Determination of phosphorus in biological samples by thermal neutron activation followed by β--counting

Phosphorus has been determined using the ^- emitter³²P by instrumental neutron activation analysis (INAA) in several NBS and IAEA standards and samples of biological origin such as human and animal blood, cancerous tissue, edible plant leaves, diets, milk samples, etc. The method involves thermal neutron irradiation for 2–10 h in a reactor followed by ^--counting on an end-window gas flow proportional counter using an aluminium filter. The results are within ±10% of the certified values in most cases.     

Determination of chromium, iron and cobalt in high-purity niobium by radiochemical neutron activation analysis

Summary Chromium, iron and cobalt were determined in niobium by radiochemical neutron activation analysis. The main steps of the technique involved the irradiation of the samples in a medium or high-flux reactor, the post-irradiation decontamination of the sample surface, a two-step separation procedure based on anion-exchange from HF and HCl medium, and counting the separated indicator radionuclides with a well-type NaI-detector. For a 42-day irradiation at a thermal neutron flux of 8×10¹³ n cm^–2 s^–1 and a sample weight of 100 mg, the limits of detection are: 10 ppt for chromium, 1.5 ppb for iron and 4 ppt for cobalt. The results obtained by this technique are compared with data obtained by radiochemical proton activation analysis and atomic absorption spectrometry.

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Bestimmung von Chrom, Eisen und Cobalt in hochreinem Niob durch radiochemische Neutronenaktivierungsanalyse

Zusammenfassung Die Hauptschritte der Methode sind die Bestrahlung der Probe in einem Mittel- oder Hochflußreaktor, eine anschließende Oberflächendekontamination und die spezifische Abtrennung der Indicatorradionuklide mittels Anionaustausch aus Flußsäure- und Salzsäure-Medium, sowie die Messung der Radionuklid-Fraktionen mit einem Natriumjodid-Detektor.Für eine 42tägige Bestrahlung mit Reaktorneutronen bei einem thermischen Fluß von 8×10¹³ n cm^–2 s^–1 konnte bei einem Probengewicht von 100 mg für Chrom eine Nachweisgrenze von 10 ppt, für Eisen von 1,5 ppb und für Cobalt von 4 ppt erreicht werden.Die mit dem Verfahren erhaltenen Ergebnisse werden mit denen der radiochemischen Protonenaktivierungsanalyse und der Atomabsorptions-Spektrometrie verglichen.

     

The role of NAA in nuclear chemistry education

One of the missions of our Institute is the promotion of basic nuclear teaching for students as well as professional teaching for workers in nuclear industry and research. For nuclear chemistry education, we present here a one day teaching course on radioactive decay and nuclear reactions, and a two or three days course based on reactor irradiation of uranium oxide, instrumental and radiochemical analysis of fission products. In the first experiment, the neutron capture is presented as an example of nuclear reaction; the neutron activation of a silver coin with a Am-Be neutron source, followed by γ-ray spectrometry, is used to identify three radionuclides of silver and to calculate their half-lives. In the second experiment, our teaching reactor is used as a neutron source with a flux about 10¹⁰ n·cm⁻²·s⁻¹ at a low thermal power (10 kW). This low flux allows us to irradiate a small uranium sample which is usable for spectrometry after a short cooling time of about two hours. The first day is reserved for instrumental analysis of the fission products and a second day for the radiochemical separation of a fission radionuclides. With these experimental results, the students have to calculate the number of fissions in the irradiated sample. On optional third day for postgraduate students is devoted to the presentation of NAA and some applications as uranium determination by the fission product spectrometry.     

Determination of fluorine in coral skeletons by instrumental neutron activation analysis

Summary A systematic and non-destructive technique is proposed for the determination of fluorine in coral samples by instrumental neutron activation analysis using the ¹⁹F(n,γ)²⁰F reaction. About 50 to 80-mg samples in polypropylene capsules were irradiated for 15 seconds in the pneumatic transfer tube system (PN-3) of JRR-3M reactor. After the irradiation at a thermal neutron flux of 1.5 ^. 10¹³ n ^. cm^{-2 .} s^-1, the coral samples and standards were cooled for 6 seconds and the g-rays emitted were measured for 15 seconds with a Ge detector. The sequence from sample irradiation to g-ray counting was performed under a computer-control mode. The analytical precision was ~5% for the JCp-1 coral standard. The present method was applied to the determination of fluorine in corals from Thailand, Okinawa and the Philippines. The advantage of one method over destructive techniques is discussed by comparing the analytical results obtained for the JCp-1 coral standard using INAA, ion chromatography and spectrophotometry. Factors that may control the levels of fluorine in corals are also discussed.     

Determination of chlorine in silicate rocks by neutron activation analysis

A simple radiochemical neutron activation analysis scheme has been developed for the determination of chlorine in silicate rocks. The method involves a 15-min thermal neutron irradiation of rock powder followed by a quick separation of ³⁸Cl as AgCl, and Ge(Li) spectrometry. Chemical yield, normally ranging between 95% and 100%, is monitored gravimetrically through the recovery of AgCl. The procedure has been tested on several geochemical standards to assess its accuracy and precision. The values obtained for standard rocks agree with the literature values. At the 100-ppm level, the analytical precision for chlorine is within ±5% (2σ).     

Determination of silver in biological reference materials by neutron activation analysis

Silver in selected, predominantly biological, reference materials (NIST SRM 1515, 1547, 1549, 1566a, 1571, 1577b, 2704, CTA-OTL-1, and Bowen’s Kale) was determined using neutron activation analysis (NAA) in two different analytical modes: instrumental NAA with epithermal neutrons (ENAA), and NAA with radiochemical separation (RNAA). The ENAA mode was based on long-time 5-hour irradiation of samples in a special Cd lined box with counting after 8-month decay. The RNAA procedure consisted in 20-hour irradiation of samples, their decomposition/dissolution by alkaline-oxidative fusion, and precipitation of AgCl including several purification steps. Both methods provided Ag contents in the analyzed reference materials consistent with certified and/or literature values down to the ng·g⁻¹ level.     

Polyurethane foam of the polyether type as a solid polymeric extractant for cobalt and iron from thiocyanate media

By combining instrumental and radiochemical neutron activation analysis, up to 47 elements including major, minor, and trace elements, have been determined in lake sediment samples. Instrumental neutron activation involving both short and long irradiations is used to determine 40 elements including most of the environmentally important ones. A radiochemical separation procedure allows the determination of 7 noble metals. The accuracy and precision of the method are 5–10%.     

Aktivierungsanalytische Bestimmung von Thallium in gesteinen

In a series of rock samples—including some USGS standard rocks—thallium was determined by thermal neutron activation analysis. After complete radiochemical purification the radioactivity of the samples was measured with conventional methane flow counters using the 97.9% β-decay and by evaluating the Hg-X-rays from 2.1% electron capture of²⁰⁴T (T=3.8y). Whith a Ge(Li) detector concentrations of 1 ppb (after 3 days irradiation at a thermal neutron flux of 6·10¹³ n·cm^?2·sec^?1) could be detected after a very simple radiochemical procedure based on ion exchange.     

Instrumental neutron activation analysis of lunar samples and the identification of primary matter in the Lunar Highlands

We describe the scheme of sequential neutron activation which was developed in our laboratory especially for the analysis of lunar samples and in which more than 50 elements are determined. Irradiations with 14 MeV, epithermal and thermal neutrons and both instrumental techniques and radiochemical separations were applied. It is shown that the achieved accuracy can compete with the best available analytical methods for most major and many trace elements. Besides the observation of “correlated elements”, the discovery of primary matter of the last accretion stage of the moon in samples from the lunar highlands is discussed in some detail.     

Determination of Macro, Micro and Ultra Micro Concentration of Some Elements in Normal and Diseased Tissues of the Bone by NAA Employing 252Cf and Reactor Neutrons

A method has been developed for the determination of elements in normal and diseased tissues of the bone employing radiochemical and instrumental neutron activation analysis. Elements such as Na, Br, Au, Sb, Sc, Fe, Zn and Cr were subjected to irradiation in ²⁵²Cf or CIRUS reactor followed by measurement of the activity on a HPGe detector coupled to a PC based MCA unit. Elements such as Co, Ca and P were subjected to radiochemical separation prior to the measurement. The statistical evaluation with respect to accuracy and precision is discussed.     

Determination of trace elements in Brazilian rice grains and in biological reference materials by neutron activation analysis

Instrumental neutron activation analysis was applied to the determination of the elements Na, K, Br, As, Rb, Zn, Co, Fe and Sc in Brazilian rice samples and in biological standards. Hg and Se concentrations were determined by using a simple radiochemical separation. The chemical procedure was carried out by means of distillation of Hg and Se in HBr medium and subsequent precipitation of selenium by sodium metabisulfite and mercury by thioacetamide. The accuracy of the instrumental and radiochemical methods was evaluated by means of analysis of the Reference Materials NBS-Bovine Liver, Bowen's Kale and NBS-Rice Flour.     

Routine activation analysis with an automatic ion-exchange apparatus

Summary The application of the automatic ion-exchange apparatus by Samsahl, to the determination of trace elements in biological, medical and environmental samples, is described. By this method it is possible to analyse for up to about 40 trace elements in various materials. Because of the large number of elements determined by this device, a flux-monitor irradiation method is applied for the quantitative determination of the various elements. Problems in the preparation of standards, determination of the radiochemical recovery, influence of different geometries in the gamma-spectroscopy, and evaluation of the data are discussed. All the steps in the analysis — irradiation, radiochemical procedure, gamma-spectroscopy and evaluation of the spectra — have been tested by use of an international biological standard reference material.

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Zusammenfassung Die Anwendung der automatischen Gruppentrennungsapparatur nach Samsahl zur Bestimmung von Spurenelementen in biologischen, medizinischen und Umweltproben wurde beschrieben. Mit Hilfe dieses radiochemischen Verfahrens ist es möglich, bis zu etwa 40 Spurenelemente in den verschiedensten Materialien nachzuweisen. Wegen der großen Anzahl der zu bestimmenden Elemente wird bei der Bestrahlung der Proben mit der Neutronenfluß-Monitor-Methode gearbeitet. Verschiedene Probleme, wie Standardzubereitung, Bestimmung der radiochemischen Ausbeuten, Einfluß der Meßgeometrie bei der Gamma-Spektroskopie und die Auswertung der Gamma-Spektren wurden diskutiert. Alle diese Schritte der Analyse werden laufend mit Standardreferenzmaterialien getestet, um systematische Fehler in der Analyse zu vermeiden.

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Presented at the International Symposium on Microchemical Techniques, May 23–27, 1977, Davos, Switzerland.     

Low-level determination of silicon in biological materials using radiochemical neutron activation analysis

Summary A new radiochemical neutron activation analysis (RNAA) method has been developed for low-level determination of Si in biological materials, which is based on the ³⁰Si(n,γ)³¹Si nuclear reaction with thermal neutrons. The radiochemical separation consists of an alkaline-oxidative decomposition followed by distillation of SiF₄. Nuclear interferences, namely that of the ³¹P(n,p)³¹Si with fast neutrons, have been examined and found negligible only when irradiation is carried out in an extremely well-thermalized neutron spectrum, such as available at the NIST reactor. The RNAA procedure yields excellent radiochemical purity of the separated fractions, which allows the measurement of the β^--activity of the ³¹Si by liquid scintillation counting. Results for several reference materials, namely Bowen’s Kale, Bovine Liver (NIST SRM 1577b), Non-Fat Milk Powder (NIST SRM 1549) and several intercomparison samples, Pork Liver-1, Pork Liver-2 and Cellulose Avicel, are presented and compared with literature values.