Determination of U and Th in tungsten by radiochemical neutron activation analysis

A radiochemical separation method using an anion exchange resin has been applied to 4N grade tungsten for determining U, Th and 4 other elements. While tungsten remained in the resin, Na, K and As were separated with 0.05M HCl and 1M HF and then U, Th and Cr were eluted with 1M HCl and 1M HF. The separation yield of neptunium (U) was influenced largely by the amount of thorium, but this influence could be neglected as the concentration of the thorium was below 0.5g/ml. The content of these elements were calculated by a single comparator method using monitors, gold and cobalt. The detection limits of U and Th are 4.0 and 1.2 ppb, respectively.     

Separation behavior of U(VI) and Th(IV) on a cation exchange column using 2,6-pyridine dicarboxylic acid as a complexing agent and its application for the rapid separation and determination of U and Th by ion chromatography

The retention behavior of U and Th as their 2,6-pyridine dicarboxylic acid (PDCA) complexes on a cation exchange column was investigated under low pH conditions. Based on the observed retention characteristics, an ion chromatographic method for the rapid separation of uranium and thorium in isocratic elution mode using 0.08 mM PDCA and 0.24 M KNO(3) in 0.22 M HNO(3) as the eluent was developed. Both uranium and thorium were eluted as their PDCA complexes within 2 min, whereas the transition and lanthanide metal cations were eluted as an unresolved broad peak after thorium. Under the optimized conditions both U and Th have no interference either from alkali and alkaline earth elements up to a concentration ratio of 1:500 or from other elements up to 1:100. The detection limits (LOD) of U and Th were calculated as 0.04 and 0.06 ppm, respectively (S/N=3). The precision in the measurement of peak area of 0.5 ppm of both U and Th was better than 5% and a linear calibration in the concentration range of 0.25-25 ppm of U and Th was obtained. The method was successfully applied to determine U and Th in effluent water samples.     

Uniformly sized molecularly imprinted polymer for d-chlorpheniramine. Evaluation of retention and molecular recognition properties in an aqueous mobile phase

Rapid separation and determination of mixtures of L-ascorbic acid, nitrite, sulfite, oxalate, iodide and thiosulfate by conventional ion chromatography is often difficult due to incomplete separation of L-ascorbic acid and nitrite from the water peak when using eluents giving short elution times for iodide and thiosulfate. Separation of the six species within about 15 min has been achieved by isocratic elution using a resin-based ion-exchange column with a carbonate eluent containing a trace amount of 1,3,5-benzenetricarboxylic acid (BTA) and fluorescence measurement of cerium(III) formed via postcolumn reactions of the separated sample species with cerium(IV). Calibration plots of peak height versus concentration were linear up to 10.0 microM (1.76 ppm) for L-ascorbic acid, 8.0 microM (0.37 ppm) for nitrite, 8.0 microM (0.70 ppm) for oxalate, 80.0 microM (10.2 ppm) for iodide and 25.0 microM (2.80 ppm) for thiosulfate, whilst the sulfite calibration was linear up to 25.0 microM (2.00 ppm) when peak area was plotted against concentration. Detection limits (defined as S/N = 3) were 18 ppb for L-ascorbic acid, 4 ppb for nitrite, 16 ppb for sulfite, 7 ppb for oxalate, 72 ppb for iodide and 37 ppb for thiosulfate. The proposed method was applied successfully to the determination of L-ascorbic acid, nitrite, sulfite, oxalate, iodide or thiosulfate in water samples.     

Instrumental neutron activation analysis of brewer's yeast

Instrumental neutron activation was used for the determination of 23 trace and minor elements in 4 different samples of brewer's yeast. Detection limits for these elements vary from 2 ppb to 100 ppm. The following average concentrations were found (ppm, dry weight): Al 597, Br 0.36, Cl 1473, Co 0.21, Cu 19, Fe 285, K 16 400, Mg 1355, Mn 8.4, Na 2330, Rb 19, Sb 0.053, Se 1.2, V 2.2 and Zn 80. NBS standard 1569 was also analyzed and the following concentrations (in ppm) were measured: Al 2300, Br 0.65, Ce 0.23, Cl 460, Co 0.26, Cr 2.12, Cu 11, Fe 707, Gd 7.1, Hf 0.13, K 15 500, Mg 1780, Mn 7, Na 510, Rb 16, Sb 0.075, Sc 0.18, Se 0.92, Th 3.7, Ti 38, U 0.49, V 4.1 and Zn 70.     

Trace elemental analysis of commercial bottled drinking water by a portable total reflection X-ray fluorescence spectrometer.

A portable total reflection X-ray fluorescence spectrometer was applied to commercial bottled drinking water containing 62 ppb (microg/L) V, 7.5 ppm (mg/L) Ca, and 1 ppm K. A dry residue, prepared by repeated pipetting and drying a 20 microL portion of drinking water on a sample holder six times, and another dry residue, prepared by pipetting and drying a 120 microL portion of the drinking water, were measured. The size of the dry residue of the drinking water was reduced by repeating the pipetting and drying. Calcium and potassium were easily detected in these two dry residues. Vanadium was detected in the dry residue prepared by repeated pipetting and drying. Vanadium, calcium, and potassium were quantified by using an internal standard, and the average quantified concentrations of V, Ca, and K were 91 ppb, 8.2 ppm, and 1.5 ppm, respectively. Although these quantified concentrations deviated from the certified concentrations (62 ppb of V, 7.5 ppm of Ca, and 1 ppm of K), it was possible for this portable spectrometer to estimate approximate concentrations.     

Determination of uranium and thorium in semiconductor memory materials by high fluence neutron activation analysis

Uranium and thorium were measured by absolute neutron activation analysis in high-purity materials used to manufacture semiconductor memories. The main thrust of the study concerned aluminium and aluminum alloys used as sources for thin film preparation, evaporated metal films, and samples from the Czochralski silicon crystal process. Average levels of U and Th were found for the source alloys to be ≈65 and ≈45 ppb, respectively. Levels of U and Th in silicon samples fell in the range of a few parts per trillion. Evaporated metal films containted about 1 ppb U and Th, but there is some question about these results due to the possibility of contamination. Operated by Union Carbide Corporation for the U.S. Department of Energy, under Contract No. W-7405-eng-26.     

Determination of thorium and uranium in hot spring and crater lake waters by neutron activation analysis

Determination of Th and U in acidic hot spring and crater lake waters was investigated by neutron activation analysis (NAA). Before neutron irradiation, Th and U were preconcentrated and separated from interfering nuclides such as alkali metals and halogens by coprecipitation with aluminium. Irradiation was carried out in two ways, viz., irradiation with Cd foil wrapping (epithermal NAA) and irradiation without Cd foil wrapping (normal NAA). The final determined values of Th and U were at ppb levels. Higher reliability of the determined values was obtained for Th than for U. It was found that epithermal NAA was more effective for the determination of these two actinides than normal NAA and was more effective for the determination of U than that of Th.     

Epithermal instrumental neutron activation analysis for the determination of gold and arsenic in Ghanaian gold tailings using conventional and anti-coincidence counting

Epithermal instrumental neutron activation analysis (EINAA) together with both conventional and anti-coincidence counting techniques were used to analyze six different gold tailing samples from Ghana for Au and As. The method involves the use of the epi-cadmium site of the Dalhousie University Slowpoke-2 reactor facility for the irradiation of the samples. After irradiation, the samples were counted directly on the detectors. The identification and quantification of the elements were done using 411 keV photopeak of ¹⁹⁸Au and both 559 keV and 657 keV photopeaks of ⁷⁶As. The precision and accuracy of the method were evaluated. Values for Au in the samples ranged from 2.48 ppm and 6.76 ppm and for As between 1,550 ppm and 3,460 ppm. The values obtained using the two counting systems were in good agreement while the anti-coincidence counting system gave values of higher precision and accuracy. The detection limit for Au were 20 and 10 ppb for the conventional and anti-coincidence spectrometric systems, respectively, and 50 ppb for As in both cases. Details of the method and results are presented.     

Radioactive ore analysis by optimized radioisotope X-ray fluorescence technique

A method for analyzing U and Th in radioactive ores by radioisotope excited X-ray fluorescence is described. For the proposed analysis, the theoretical and experimental factors that affect the sensitivity of the radioisotope XRF technique were investigated. Minimum detection limits of 13 ppm and 108 ppm can be achieved for U and Th, respectively, with a total counting time of 1000 s on a powdered ore sample. Results obtained in the analyses of radioactive ores from Turkey and BL-5 candidate reference uranium ores from CANMET (Canada Centre for Mineral and Energy Technology) are reported.     

Determining 234Th and 238U in rocks, soils, and sediments via the doublet gamma at 92.5 keV

Efficient and accurate measurements of uranium (U) and U-series radionuclides in earth's materials are needed to assess its environmental impact, reconstruct geochemical histories, and quantify heat production in the crust. To date, measurements of 234Th and 238U by gamma spectrometry have relied on the quantification of 234Th gamma emissions at approximately 63 keV (absolute intensity = 3.7%) and the (234m)Pa gamma at 1001 keV (absolute intensity = 0.84%). However, use of the 63 keV emissions can be hampered by 232Th interferences and self absorption, and the 1001 keV photon has a very low yield. Here we describe the effective use of the 234Th doublet gamma emission at approximately 92.5 keV (total absolute intensity = 4.8%) for 234Th and 238U measurements. This doublet has been largely ignored because of its proximity to the Th K(alpha1) (93.3 keV) and thus its vulnerability to a Th self-fluorescence interference. We demonstrate that additions of U and 40K to a Th ore sample do not increase the count rate at 92-93 keV above that which would be expected from the associated additions of U and 234Th. We also show that the Th self-fluorescence interference appears to be an anomaly associated only with the analysis of relatively thick (>1 mm) Th minerals, and suggest that fluorescence will not complicate the 92-93 keV region in most environmental samples. A review of decay data reveals that Th K(alpha1) X-rays associated with the decay of 235U and 228Ac can significantly interfere with quantification of the 92.5 keV 234Th doublet. We show that simple experimentally-derived correction factors for these X-rays can be used to accurately determine 234Th using its strongest gammas, resulting in higher count rates and smaller self-absorption corrections relative to the traditional analytical lines. Total 1 sigma analytical error associated with U measurements at 92.5 keV ranged from 1 to 9% and is dominated by the relative size of the 228Ac interference. Detection limits for U in environmental samples using this technique are on the order of 50 ppb.     

Determination of uranium and thorium concentration in some Egyptian rock samples

Uranium (U) and thorium (Th) isotopes and their several radioactive descendants found in soil, rock, water, plants, air, etc., contribute to the natural radiation exposure of the population. Phosphate rocks are really rich natural sources of uranium and thorium among the other minerals forming the earth's crust. U and Th concentrations in some Egyptian phosphate samples were determined using a nuclear track registration methodology and -ray spectroscopy. The resulting latent tracks from all -decaying isotopes in both U and Th series were recorded in plastic detectors. A uniquely sensitive polycarbonate CR-39 nuclear detector was used. Results showed that the U and Th concentration in the samples studied range from about 4.0 up to 35.0 ppm and from 11.0 to 124.0 ppm, respectively. Results are discussed within the frame work of track formation methodology in plastic and -ray spectroscopic analysis.     

Untersuchungen an Geologischen Materialien Durch Messung der Natürlichen Gamma-aktivität

Investigations of natural activity of several geological materials by γ-spectrometry using a Ge(Li)-detector are described. The determination of thorium and uranium contents is possible up to minimum concentrations of about 10 ppm Th and 1 ppm U. The results of this method are compared with results of different methods of activation analysis. In the most cases the agreement is very well. If the decay-chain of²³⁸U is not in equilibration, it is possible to estimate the geological oldness of the sample in a range between about 20 000 and 200 000 years.     

Liquid chromatography/electrospray tandem mass spectrometric analysis of incurred ractopamine residues in livestock tissues

Ractopamine HCl is a beta-adrenergic agonist (beta-agonist) recently approved by the U.S. Food and Drug Administration, but not other governmental agencies, for use in finishing swine. For these reasons, it was important to develop and validate mass spectrometric methods for the detection and confirmation of ractopamine residues in livestock marker tissues. Incurred tissues in cattle, sheep, turkeys, and ducks were generated during 7-day ractopamine feeding (20 ppm in diets) periods. Disposition of ractopamine residues in liver and pigmented retinal epithelium was determined in animals slaughtered with withdrawal periods of 0, 3, and 7 days. Ractopamine residues, purified using solid-phase extraction, were measured using liquid chromatography (LC) and electrospray with detection by tandem mass spectrometry (MS/MS) in the multiple reaction-monitoring (MRM) mode. Total ractopamine residues (parent ractopamine + hydrolyzed conjugates) in liver were detected in all species on withdrawal day 0 (2-97 ppb) and were greatly diminished in all species by withdrawal day 7 (<1 ppb). Bovine and ovine retina had lower levels of ractopamine (0.5-3 ppb) than liver, and occular residues increased with withdrawal time, suggesting redistribution into this tissue. Lower limits of quantification were found to be approximately 0.1 ppb in liver and retina. Incurred ractopamine residues were confirmed by the precise and accurate agreement of MRM intensity ratios of diagnostic fragment ions (m/z 284, 164, and 121) from the protonated molecule between ractopamine residues in incurred samples and an authentic ractopamine standard. The limits of confirmation in liver and retina using recognized acceptance criteria were below 1 ppb. The high sensitivity and specificity for measurement and confirmation of ractopamine residues suggests this method will be applicable for regulatory residue surveillance programs.     

Copper(II) determination by means of a thermometric method based on its catalytic effect on the hydrazine-hydrogen peroxide reaction

A new catalytic-thermometric method for Cu(II) determination at ppb levels has been established based on the hydrazine-hydrogen peroxide redox reaction. The reaction rate is obtained from the temperature-time curve and shows two linear response zones, between 15–200 ppb and 0.1–0.9 ppm, with a relative standard deviation of 2.0% and 2.2%, respectively. Only 20 ppm of Pb(II) and Fe(III), 1 ppm of Mn(II) and 5 ppb of Co(II) interfere. Interferences of Pb(II) and Fe(III) can be eliminated by the use of maskings. The proposed method can be applied to determine Cu(II) in several samples. In the present paper, this method has been applied to determine Cu(II) in wine.     

A preliminary investigation on the determination of lanthanoids, thorium and uranium in brine and deposit of a salt lake in China

A brine sample and two deposit samples of a salt lake in China were analyzed for their contents of lanthanoids (Ln's), thorium and uranium by neutron activation analysis. Five Ln's were determined at sub ppb levels. Th and U contents were at about the same levels as those of Ln's. The lanthanoid abundance patterns (Ln pattern) of the three samples are similar to each other, each having a negative slope in the light Ln region. There seems no substantial difference in distribution between the solution (brine) and solid (deposit) phases among Ln's.     

Th,U and trace elements determination in Egyiptian Lake sediments by INAA and laser fluorimetry

A study was undertaken to determine element concentrations in Aswan High Dam Lake sediments. Sediment samples were collected from 40 to 500 km upstream of the dam to follow the sedimentation process and the distribution of Th, U and the trace elements in the lake. INAA was applied for the determination of Sm, Ce, Lu, Th, Cr, Yb, Au, Hf, Ba, Nd, Cs, Tb, Sc, Rb, Fe, Zn, Co, Eu, and Sb, while Laser Fluorimetry was applied for U determination. The accuracy and the reproducibility of the techniques were tested with IAEA standard materials (SL, Soil-7). The U values ranged from 4 ppm to 18 ppm, Th values were between 2 and 10 ppm, and showed a very good correlation with the rare earth elements and Fe. The distribution of most of the elements in the lake follows the same trend as the distribution of the clays in the sediments. Ba showed a negative correlation with most of the elements under investigation.Paper presented at the 3th International Conf. on Nuclear and Radiochemistry (NRC-3), Vienna, 1992.     

Radioactivity levels of <Superscript>238</Superscript>U and <Superscript>232</Superscript>Th,the α and β activities and associated dose rates from surface soil in Ulu Tiram,Malaysia

A survey was carried out to determine terrestrial gammaradiation dose rates, the concentration level of ²³⁸U and ²³²Th and α and β activities for the surface soil in Ulu Tiram, Malaysia A 125 measurements were performed using a NaI(T1) gamma-ray detector with crystal size of 1″ × 1″ on 15 soil samples collected from the site area about 102 km^{2 238}U and ²³²Th concentrations were determined in soils by using hyper pure germanium (HPGe) gamma-ray spectrometry. The activity of α and β from the surface soil was counted by using alpha beta counting system. The average value of ²³⁸U and ²³²Th concentrations in soil samples collected are 3.63±0.39 ppm within the range of 1.74±0.20 to 4.58±0.48 and 43.00±2.31 ppm within the range of 10.68±0.76 to 82 10±4.01 ppm, respectively. The average estimate of α and β activity in soil samples collected are 0.65±0.09 Bqg⁻¹ and 0.68±0.08 Bqg⁻¹, respectively. The average of terrestrial gamma-radiation dose rates measured in Ulu Tiram was found to be 200 nGy h⁻¹, within the range of 96 to 409 nGy h⁻¹. The population weighted outdoor annual effective dose was 1.2 mSv.     

Distribution of uranium in sediment of creek ecosystem

The present study was carried on distribution of uranium isotopes and Thorium in marine sediment from creek of Mumbai Harbour Bay (MHB) using radiochemical separation followed by alpha spectrometry. The activity concentration of uranium and thorium in sediment of MHB has ranged between 1–4 and 1.8–4.5 ppm respectively. The activity ratio of ²³⁴U/²³⁸U in sediment was found close to unity at most of the locations of creek suggesting a conservative behaviour. The observed Th/U ratio (0.9) in comparison to global Th/U ratio (?3.5) in the creek sediment indicates that it receives low radiogenic nature of terronenous input.     

Gamma-ray spectroscopic and PIXE analysis of selected samples from the phosphorite deposits of Northwestern Saudi Arabia

Phosphorite deposits from northwestern Saudi Arabia were analyzed by natural radioactivity measurements to detect the presence of radioactive elements. PIXE was used to obtain an average elemental composition of these deposits. From the analysis of radiations from ²³⁸U, ²³²Th and ⁴⁰K isotopes, the samples were found to contain U, Th and K in concentrations up to 130 ppm, 30 ppm and 2.5 wt%, respectively. PIXE showed the presence of a number of trace elements such as Ca, V, Cr, Fe, Ni, Cu, Zn, As, Sr, Y and U in concentrations ranging from a few ppm to several hundred ppm. The occurrence of these radioactive and non-radioactive elements are discussed for their geological significance in the phosphorite deposits.     

Preconcentration of U(VI) from aqueous solutions after sorption using Sorel’s cement in dynamic mode

Summary Mg(OH)₂ was identified as a component of Sorel’s cement being a very strong sorbent for uranium. Sorel’s cement is a mixture of MgO, MgCl₂ and water. The optimal conditions for the adsorption of U(VI) was studied by the batch method. A contact time of 2 hours was found to be optimum. Maximum U(VI) uptake was observed in a pH range of 5.5-6.5 with a sorption constant of K_ads = 0.9 h^-1 at initial concentration of 20 ppm. Polypropylene columns filled with 2 g of Sorel’s cement at a mesh size of 35 were used for the preconcentration of uranium by passing 8 l of water containing 10 ppb U(VI). A flow rate of 0.25 ml/min and a bed height of 5 cm were found to be the optimum for the U(VI) separation. A 5 wt% triphenylphosphine oxide solution in toluene was used as an organic solvent for the separation of uranium from interfering elements such as iron(III) and thorium(IV), prior to spectrophotometric analysis. The determination of U(VI) was accomplished by adding Arsenazo III as a coloring reagent to the solution and using a UV-160A spectrophotometer.