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.

     

Determination of arsenic,scandium, chromium,cobalt and nickel in asbestos by neutron activation analysis

Arsenic, scandium, chromium, cobalt and nickel were determined by neutron activation analysis in various Chrysolite-Asbestos from Canada, Russia, Italy in an asbestos plate, and in dry, as well as in wet manufactured asbestos. Following concentration values were found: for As 0.01–5.5 ppm, for Sc 5.4–14.80 ppm, for Cr 79.5–918.8 ppm, for Co 10.8–80.9 ppm, for Ni 148–1786 ppm. Statistically significant differences /t=0.05/ in contents of As, Sc, Cr, Co and Ni were detected in the different samples of asbestos. The concentration of As and Cr in Italian asbestos were considerably higher than in Canadian chrysolite.     

Determination of selenium in nickel and cobalt concentrates applying epithermal neutron activation analysis

The physicochemical association of plutonium in soil near the Subsurface Disposal Area (SDA) at the Idaho National Engineering and Environmental Laboratory (INEEL) has been determined using selective sequential extraction techniques. Our results suggest that plutonium in surface soils is associated primarily with the hydrous oxide coatings of the soil (37±5.3%). Appreciable amounts of plutonium were also removed with the organic matter (22±2.8%) and carbonates (13±3.1%). On the other hand it appears that plutonium association with the soluble and exchangeable components of the soil is relatively small (>4.0%). The remainder of plutonium (21±4.7%) is tightly bound to the refractory silicate residue of the soil. Relatively little plutonium is available for physicochemical mobilization from the soil under the present prevailing conditions of the INEEL site.     

Determining trace amounts of nickel in plant samples by neutron activation analysis

Neutron activation analysis of plant samples for trace amounts of nickel has applications in various fields. Landsberger and Robinson (Trans Am Nucl Soc 102:187–188, 2010) found their measurement of the concentrations of nickel for different NIST reference materials to be significantly greater than the certified values when measuring nickel from the 810.8 keV gamma ray that comes from ⁵⁸Co from the ⁵⁸Ni(n,p) reaction. They determined that this overestimation was due to a significant interference by the presence of ¹⁵²Eu at 810.5 keV, and presented a method for correcting this interference. Their method involved a long thermal irradiation and correction of gamma ray counts based on the 1,408 keV belonging to ¹⁵²Eu. This paper presents an alternative approach, which involves irradiating the samples with epithermal neutrons, which suppressed the ¹⁵²Eu to the point of being negligible for samples with low levels of europium. Both methods were determined to work well for the identification of nickel concentrations by neutron activation analysis.     

Neutron activation analysis of some trace elements /selenium,chromium, cobalt and nickel/ in the blood of vitiligo patients

Samples of full blood of vitiligo patients and those of control persons were analyzed for Se, Cr, Co and Ni contents by neutron activation analysis. The concentrations are reported in ppm/dry weight. The results showed that the Se and Co levels were significantly higher in the blood of vitiligo patients while the increase of Cr and Ni was not significant as compared to the controls.     

Determination of chromium in blood by neutron activation analysis

A procedure for the determination of chromium in blood has been developed with a sensitivity of 5×10⁻³ μg Cr. Dried blood was irradiated with a neutron flux of 10¹² n·cm⁻²·sec⁻¹ in the VVRS reactor for 4 weeks, then the sample was mineralized and the chromium isolated by extraction as perchromic acid. The determination of the chromium content was accomplished by measuring the 0.32 MeV gamma energy of⁵¹Cr. In order to make correction for the interfering reaction⁵⁴Fe(n,α)⁵¹Cr, the formation of chromium from high-purity iron was investigated. The chromium content of the blood samples was between 1.03×10⁻² and 5.2×10⁻² ppm Cr.     

Determination of arsenic,chromium, mercury,selenium and zinc in tropical marine fish by neutron activation

Determination of arsenic, chromium, mercury, selenium and zinc in several commonly consumed tropical marine fishes have been carried out by neutron activation followed by radiochemical separation to remove the interfering activities of sodium, potassium, bromine, and phosphorus, etc., in order to establish the baseline data and to measure the levels of contamination, if any. The results of this study positively indicate that the marine fishes of Bangladesh have concentrations much below the permissible levels for these toxic elements. A radiochemical scheme for the separation of seven trace elements in biological material is also presented in this paper.     

Determination of trace amounts of copper and selenium in biological samples by chemical separation prior to neutron activation analysis

It was found that Cu and Se can be relatively easily and accurately determined by preconcentration of Cu and Se prior to the determination by neutron activation analysis with the short-lived IRN's (Indicator Radionuclides)⁶⁶Cu and^77mSe. The method consists of wet acid digestion followed by coprecipitation with lead tetramethylenedithiocarbamate. The precipitate was collected, irradiated and counted. The validity of the method was confirmed both by internal checks, as the measurement also by⁷⁵Se and by the use of two reference material of biological origin. The limit of detection was found to be 20 ng Se and 50 ng Cu for a 0.1 g sample.     

Determination of arsenic,cadmium and zinc in river water by neutron activation analysis

A concentration apparatus has been developed for the determination of As, Cd and Zn in water by neutron activation. The preconcentration technique used for this purpose is based on the retention of As, Cd and Zn on the Rexyn 201 resin at pH 10. The apparatus used minimizes the manipulations needed for preconcentration and contamination by trace elements present in reagents. Eleven samples of water from rivers in the Montreal region were analyzed and the following concentrations were found (in μg/1): As 0.86–1.95, Cd 0.61–0.98 and Zn 4.6–12.9.     

Determination of trace amounts of titanium and vanadium in human blood serum by neutron activation analysis: Coprecipitation with Pb/PDC/2 or Bi/PDC/3

The concentrations of titanium and vanadium in biological material, human blood serum, were determined by neutron activation analysis, using a prior coprecipitation with Pb/PDC/₂ as well as Bi/PDC/₃. Titanium and vanadium were quantitatively determined by measuring the gamma ray photopeaks of the short-lived radionuclides⁵¹Ti /5.8 min/ and⁵²V /3.75 min/, respectively. The concentrations ranged from 105.7 to 131.9 ng ml^–1 /Ti/ and from 1.30 to 6.05 ng ml^–1 /V/. The detection limits for titanium and vanadium under the present experimental conditions were found to be 70 and 0.7 ng for 1 ml of blood serum sample, respectively.     

Dithiocarbamate extraction of trace amounts of selenium from biological samples for neutron activation analysis

A three-step method has been developed for extracting trace amounts of selenium from biological samples for neutron activation analysis /NAA/. After acid digestion, the sample is first extracted with lead diethyldithiocarbamate at pH 4 to remove a number of interfering elements. Next, selenium is extracted with sodium diethyldithiocarbamate into chloroform at pH 1.5. Finally, selenium is back-extracted with concentrated nitric acid for NAA. Analysis of selenium extracted from four standard reference materials resulted in excellent agreement with the certified values of selenium concentration. A detection limit of 0.05 g has been achieved.     

Determination of trace cadmium and other elements in bone by epithermal neutron activation analysis

Epithermal neutron activation analysis (ENAA) was applied to measure quantitatively Cd and other elements in bone samples from control and Cd-fed rats. This method was found to be non-destructive to the bone samples, with no sign of radiolytic charring and was sensitive enough to detect and quantify Cd in bone samples at normal levels for mammals (viz. 0.5–1.0 g/g) and higher. Two different thermal neutron shield materials were utilized, namely cadmium and boron. The boron shield resulted in a 27% improvement in the detection limit of Cd in bone. The accuracy of ENAA for Cd was assessed by intercomparison with electrothermal atomic absorption spectrophotometry (ETAAS), and the results were in fair agreement (±23%) with those from ENAA.     

Determination of iron, nickel, chromium and vanadium by means of redox and ion-exchange columns

Redox and anion-exchange columns have been used to separate and determine iron, nickel, chromium and vanadium in solution. The anion-exchange columns provide some of the separations, and the redox columns are used for the determination of the iron, chromium and vanadium. The chromium and vanadium may be determined in the presence of the iron by adjustment of the acidity in the redox column. By using a column "memory" technique, titration of the actual metal solution has been avoided. The method shows some advantages over conventional methods.     

The simultaneous determination of vanadium,chromium, manganese,iron, cobalt,nickel, copper and zinc in sea water by x-ray fluorescence sectrometry

A procedure is described for the determination of microgram quantities of the elements vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc in sea water. Separation and concentration of these elements from a large salt matrix, in order to prevent interferences in the subsequent X-ray fluorescence spectrometry, is achieved by continuous solvent extraction. Ammonium pyrrolidine dithiocarbamate is used as a chelating agent, and the chelated trace elements are quantitatively extracted at a pH of ca. 2.5 into methyl isobutyl ketone. Detection limits of 0.14 μg or better are obtained when a 600-sec counting period is used for X-ray fluorescence spectrometry.     

Semiquantitative determination of micro amounts of iron,copper, cobalt,nickel, and zinc in blood and tissue by circular thin-layer chromatography

Summary A semiquantitative method for the determination of iron, copper, cobalt, nickel and zinc is described which is based on circular thin-layer chromatographic technique. The error is minimized to ± 5% and interference of about 40 metal ions is removed by solvent extraction. The application of the method has been demonstrated by the determination of these metal ions in human blood and tissue and the method is suggested for the study of airborne particulates.

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Zusammenfassung Ein halbquantitatives Verfahren zur Bestimmung von Eisen, Kupfer, Kobalt, Nickel und Zink auf dünnschicht-ringchromatographischem Wege wurde beschrieben. Der Fehler wurde auf ±5% eingeschränkt und die störende Wirkung von etwa 40 Metallionen durch Lösungsmittelextraktion beseitigt. Die Anwendbarkeit des Verfahrens für die Bestimmung in menschlichem Blut und Gewebe wurde gezeigt bzw. für die Untersuchung atmosphärischer Verunreinigungen empfohlen.

     

A definitive method for the determination of trace amounts of cobalt in biological materials by neutron activation analysis

A new, very accurate (definitive) method for the determination of trace amounts of cobalt in biological materials has been devised. The method is based on combination of neutron irradiation with quantitative and selective post-irradiation separation of cobalt from all accompanying radionuclides followed by measurement by -ray spectrometry. Column chromatography in which owing to addition of Co carrier the course of separation can be followed visually is the key element of the separation scheme. Several criteria have been formulated which must be simultaneously fulfilled in order to acknowledge the result as obtained by a definitive method. The high accuracy of the method has been demonstrated by the analysis of several certified reference materials of widely different Co contents.     

Simultaneous determination of nickel and cobalt traces by neutron activation analysis

Nickel and cobalt traces may be determined by measuring the ⁵⁸Co and ⁶⁰Co activities produced in a nuclear reactor. Solvent extraction of cobalt, and γ-spectrometry on the extracted phase allow a rapid and simple analysis of both metals. The method is applied to the determination of nickel (100–0.2 p.p.m.) and cobalt (0.15–0.001 p.p.m.) in various materials (petroleum, polyphenyls, aluminium).     

Determination of arsenic, cadmium, cobalt, chromium, lead, molybdenum, nickel, and selenium in fertilizers by microwave digestion and inductively coupled plasma-optical emission spectrometry detection: collaborative study

There is increasing regulatory interest in the non-nutritive metals content of fertilizer materials, but at present there is no consensus analytical method for acid digestion and instrument detection of those elements in fertilizer matrixes. This lack of method standardization has resulted in unacceptable variability of results between fertilizer laboratories performing metals analysis. A method has been developed using microwave digestion with nitric acid at 200 degrees C, followed by inductively coupled plasma-optical emission spectrometry instrument detection, for the elements arsenic, cadmium, cobalt, chromium, molybdenum, nickel, lead, and selenium. The method has been collaboratively studied, and statistical results are here reported. Fourteen collaborators were sent 62 sample materials in a blind duplicate design. Materials represented a broad cross section of fertilizer types, including phosphate ore, manufactured phosphate products, N-P-K blends, organic fertilizers, and micro-nutrient materials. As much as possible within the limit of the number of samples, materials were selected from different regions of the United States and the world. Limit of detection (LOD) was determined using synthetic fertilizers consisting of reagent grade chemicals with near zero levels of the non-nutritive elements, analyzed blindly. Samples with high iron content caused the most variability between laboratories. Most samples reasonably above LOD gave HorRat values within the range 0.5 to 2.0, indicating acceptable method performance according to AOAC guidelines for analyses in the mg/kg range. The method is recommended for AOAC Official First Action status.     

锌电解液中痕量铜、镉、镍和钴的快速同时测定

研究了丁二酮肟 氨 氯化铵 柠檬酸钠 明胶 抗坏血酸体系中Cu(Ⅱ )、Cd(Ⅱ )、Ni(Ⅱ )和Co(Ⅱ )的络合物吸附波 ,建立了同时、快速测定锌电解溶液中这些痕量元素的新方法。Cu(Ⅱ )、Cd(Ⅱ )、Ni(Ⅱ )和Co(Ⅱ )分别在 - 0 44V、- 0 76V、- 1 0 7V和 - 1 2 4V左右产生灵敏的络合物吸附波。信噪比为 3时 ,其检测限分别为 1 0× 1 0 - 8mol/L、1 3× 1 0 - 8mol/L、2 9× 1 0 - 1 0 mol/L和 3 6×1 0 - 1 1 mol/L。铜、镉、镍和钴的浓度分别为 2 0× 1 0 - 8mol/L～ 2 0× 1 0 - 5 mol/L、3 0× 1 0 - 8mol/L～ 3 0× 1 0 - 5mol/L、5 4× 1 0 - 1 0 mol/L～ 5 4× 1 0 - 7mol/L和 6 8× 1 0 - 1 1 mol/L～ 6 8× 1 0 - 8mol/L时 ,与相应峰电流之间有良好的线性关系。方法已用于锌电解液中铜、镉、镍和钴的快速同时测定 ,相对标准偏差分别小于或等于 4 7%、5 1 %、4 9%和 5 3 %。     

Determination of vanadium in human serum by neutron activation analysis

Vanadium in serum has been investigated by the aid of neutron activation analysis (8 min irradiation at 8·10¹³ n·cm⁻²·s⁻¹ in the reactor FR-II of the Kernforschungszentrum in Karlsruhe). The lyophilized samples were dry-ashed before irradiation and the⁵²V activity extracted after irradiation. The values for V in the sera of 22 healthy males ranged from 0.029–0.939 ng V·ml⁻¹. There is a real assumption that some of the high figures are due to persons being contaminated with V. The 18 healthy females yielded a mean value of 0.033±0.012 ng V·ml⁻¹ for 17 of them and one additional value of 0.139 ng V·ml⁻¹. These V-data are the lowest ever reported in the literature. The analyses of two packed blood cell samples yielded 0.031 and 0.020 ng·g⁻¹, indicating that about 68% of the total V in blood is present in serum. There was no correlation between the V-content and age, nor between the V-content and the cholesterol, triglycerides or the lipoprotein fractions in serum.