Ultra-sensitive determination of K, Th, U and other trace impurities in liquid organic scintillators by NAA

We present a NAA method to determine ultratraces of K, Th, U and other trace impurities in liquid organic scintillators, which are known as ultrapure detector materials for neutrino or dark matter experiments. A combined optimization of relevant factors for sensitive NAA has been realized, leading to a sensitivity for U down to 10⁻¹⁶g/g. Samples of 250 ml have been irradiated up to 120 h at a thermal neutron flux of 5–8·10¹²·n·cm⁻²·s⁻¹. Acidic extraction, wet ashing and TBP-extraction are used for radiochemical separations. Finally, coincidence techniques are applied for increased sensitivity.     

Preconcentration and separation of trace amounts of palladium using dithiooxamide functionalized chelating resin followed by its determination using radiotracer technique

The work describes a procedure of preconcentration and separation of trace amounts of Pd(II) by solid phase extraction of the metal ion by dithiooxamide groups incorporated into a matrix of polystyrene-divinylbenzene whereas the determination of palladium has been carried out by radiotracer technique using ¹⁰⁹Pd (T _1/2 = 13.43 hr, E _γ = 311, 647 keV). The experiments were carried out using both batch method and column operation. Parameters such as the amount of resin, effect of pH, equilibration rate, sorption and desorption of metal ions have been studied. The maximum sorption capacity for palladium was found to be 0.10 mmol·g⁻¹ at pH 6.0. The method is rapid, has a good accuracy and can be used routinely.     

Reagent-loaded and unloaded polyurethane foam as preconcentration matrix in neutron activation analysis

Loaded and unloaded polyurethane foams were examined as a preconcentration matrix in combination with neutron activation analysis. The structure of the foamed polymer is not damaged by short irradiation periods. However the foam skeleton degraded after irradiations for one hour or longer in a neutron flux of 3·10¹³ n ·cm⁻²·s⁻¹. The presence of tin as a major impurity in the polyether-type foam has been detected. This may affect the sensitivity of determination of the relatively short lived isotopes of the elements collected on the foam. On the other hand the polyester-type foam was found to contain only very low amounts of tin. Antimony, indium, gold and mercury collected on the foams were determined with reasonable accuracy.     

Determination of cadmium and lead in high purity uranium compounds by flame atomic absorption spectrometry with on-line micro-column preconcentration by CL-7301 resin

An on-line solid phase micro-column extraction and determination system for trace Cd and Pb in nuclear fuel grade uranium compounds was established. The preconcentration of trace elements Cd and Pb from uranium compounds was achieved by adsorbing Cd and Pb on CL-7301 resin in hydroiodic acid media, while the uranyl ion passed through. The method coupled with flame atomic absorption spectrometry (FAAS) was applied to analysis trace Cd and Pb in real samples. The preconcentration factors obtained by this method were 320 and 180 each for Cd and Pb, respectively. Under the optimized conditions, the detection limits corresponding to three times the standard deviation of the blank were found to be 0.13 ng·mL⁻¹ and 0.37 ng·mL⁻¹ for Cd and Pb, respectively. The relative standard deviation (RSD) and the recoveries of standard addition (spiked with 1–5 ng of Cd and Pb) were of <5% (n = 10) and 96.2%–102.3%, respectively. Precision was also evaluated and found to be ≤4.3% (N = 11). The proposed method was successfully used for the determination of trace Cd and Pb in commercially available uranium compounds (e.g., uranyl acetate and triuranium octoxide).     

Characterization of trace elements in medicinal herbs by instrumental neutron activation analysis

Medicinal herbs are often used as alternative medicines for healing and controlling some diseases in the world. This study focuses on the content of heavy and trace elements of some widely consumed herbs in Libya. Nine most popular herbs were analyzed by k ₀-instrumental neutron activation analysis. All the samples, SRM and flux monitors were irradiated for 7 and 10 hours under thermal neutron flux of 1.3·10¹³ cm⁻²·s⁻¹ at Tajoura nuclear reactor. In total, 33 elements were analyzed in different herbs. The variations in the concentration of the elements are attributed to soil composition and the climate in which the plant grows. The study showed that the toxic elements found in the samples were below the levels prescribed by health regulations. The precision and the accuracy of the results were evaluated by analyzing the reference materials Pine Needles SRM 1575 and Citrus Leaves SRM1572.     

Neutron activation analysis of rare earth impurities in metallic uranium

A method with a sensitivity of 2·10⁻⁷ to 1·10⁻¹⁰% has been developed for determining Yb, Ho, Dy, Gd, Eu, Sm and La impurities in metallic uranium by means of neutron activation. The method is based on a preliminary chromatographic separation of the total amount of rare earth elements from uranium by passing the solution in sulphuric acid through KU-2 cation exchange resin and eluting the traces of uranium retained by the resin with a solution of ascorbic acid. The rare earth impurities are then eluted from the resin with 4–5N HCl, evaporated, and irradiated for 20 hours with a neutron flux of 1.2·10¹³ n·cm⁻²·sec⁻¹. Subsequently the traces of the rare earth elements are co-precipitated with Fe(OH)₃, dissolved in concentrated HCl and separated from the iron and other impurities by passing the solution through Dowex 1X8 anion exchange resin in the chloride form. The individual rare earth elements are then separated from each other using KU-2 cation exchange resin and a solution of ammonium α-hydroxyisobutyrate as the eluant.     

Rare-earth elemental analysis of banded iron-formations by instrumental neutron activation analysis

Representative banded iron-formations (BIFs) from various locations of the eastern Indian geological belt were investigated by instrumental neutron activation analysis (INAA). After pre-concentration, irradiation was carried out using a neutron flux of 5.1·10¹⁶ m⁻²·s⁻¹, 1.0·10¹⁵ m⁻²·s⁻¹ and 3.7·10¹⁵ m⁻²s⁻¹, with thermal, epi-thermal and fast neutrons, respectively. The activities in these samples were measured by a HPGe detector. Ten rare-earth elements, such as La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu, have been qualitatively identified and quantitatively estimated in these samples. The present investigation is an example of employing a pre-concentration method for high iron-containing ores prior to neutron activation analysis.     

Determination of zinc in water samples by flame atomic absorption spectrometry after homogeneous liquid-liquid extraction

In this study, a new and simple homogeneous liquid-liquid extraction (HLLE) method based on a pH-independent phase-separation process was developed using a ternary solvent system [water-tetrabutylammonium ion (TBA ⁺)-chloroform] for the preconcentration of Zn²⁺ ions. A Schiff’s base ligand was used as the chelating agent prior to Zn²⁺ ions extraction. Flame atomic absorption spectrophotometry using acetylene-air flame was used for the quantification of analyte after preconcentration. The phase separation occurred due to ion-pair formation of TBA and perchlorate ion. The sedimented phase was then separated using a 100 μL micro-syringe and diluted to 1.0 mL with ethanol. The sample was introduced into the flame by conventional aspiration. After the optimization of complexation and extraction conditions such as pH 9.0, [ligand] = 1.0 × 10⁻⁵ M, [TBA⁺] = 2.0 × 10⁻² M, 100.0 μL of [CHCl₃] and [CLO₄⁻] = 2.0 × 10⁻² M, a preconcentration factor of 100 was achieved for only 10 mL of the sample. The relative standard deviation was 2.3% (n = 10). The limit of detection was sufficiently low and at ppb level. The proposed method was applied to the extraction and determination of Zn²⁺ in natural water samples with satisfactory results.     

Fast-neutron activation analysis with short-lived nuclides

At the GKSS Research Center Geesthacht, a new 14 MeV activation facility—a 5·10¹² n/s neutron generator combined with a fast rabbit system (KORONA)—is being installed. Homogeneous neutron flux at a level of 5·10¹⁰ n·cm⁻²·s⁻¹ and sample transfer times of 140 ms to a 16m distant detector station are characteristic features of the facility described in the paper. With special consideration of short-lived nuclides and including cyclic activation, the analytical prospects with the intense neutron source are discussed, and sensitivities for 78 elements are presented.     

Alternative chromatographic processes for no-carrier added 177Lu radioisotope separation Part I. Multi-column chromatographic process for clinically applicable

The conventional multi-column solid phase extraction (SPE) chromatography technique using di-(2-ethylhexyl)orthophosphoric acid (HDEHP) impregnated OASIS-HLB sorbent based SPE resins (OASIS-HDEHP) was developed for the separation of no-carrier added (n.c.a) ¹⁷⁷Lu from the bulk quantity of ytterbium target. This technique exploited the large variation of lutetium metal ion distribution coefficients in the varying acidity of the HCl solution-OASIS-HDEHP resin systems for the consecutive loading-eluting cycles performed on different columns. The production batches of several hundred mCi n.c.a ¹⁷⁷Lu radioisotope separated from 50 mg Yb target activated in a nuclear reactor of medium neutron flux (Φ = 5·10¹³ n·cm⁻²·s⁻¹) were successfully performed using the above mentioned separation technique. With the target irradiation in a reactor of thermal neutron flux Φ = 2·10¹⁴ n·cm⁻²·s⁻¹ or the parallel run of several separation units, many Ci-s of n.c.a ¹⁷⁷Lu can be profitably produced. The OASIS-HDEHP resin based multi-column SPE chromatography technique makes the separation process simple and economic and offers an automation capability for operation in highly radioactive hazardous environments.     

Experimental sensitivities for 3 MeV neutron activation analysis

The experimental sensitivity for 72 different elements using 3 MeV neutron activation has been investigated. Using a 200 kV Cockcroft-Walton neutron generator with a 3 MeV neutron flux of about 1.5·10⁶n·cm⁻²·sec⁻¹, γ-ray spectra of 51 elements were obtained with a sufficient number of photopeak counts for sensitivity calculations using a photopeak integration method. A useful table summarizing the sensitivity results is given. That 3 MeV neutron activation analysis is practical, is demonstrated by the experimental sensitivities obtained. Guest worker from the Institute of Nuclear Techniques, Academy of Mining and Metallurgy, Krakow, Poland, at the National Bureau of Standards, 1968–1969.     

Determination of trace elements Cd,Co, Mo,Se, Ti and V in natural waters by neutron activation analysis

The concentration of cadmium, cobalt, molybdenum, selenium, titanium and vanadium in natural water was determined by neutron activation analysis, using a prior preconcentration by a coprecipitation. The preconcentration of these trace elements was accomplished by converting the dissolved trace ions into the pyrrolidine dithiocarbonate (PDC) chelates, followed by coprecipitation on Bi as well as Pb-PDC chelates. This technique has been applied to the elements in natural waters: fresh water and sea waters (Mediterranian and Dead Sea).     

Gallium determination in biological samples

A sensitive, simple and time-saving method has been developed for the neutron activation analysis of gallium at concentrations around 10⁻⁴ ppm in biological tissues. After a 24-hour irradiation in a thermal neutron flux of 2.8·10¹³ n·cm⁻²·s⁻¹ and a purification by ion-exchange chromatography to eliminate troublesome elements such as sodium, iron and copper, the⁷²Ga activity is measured with enough accuracy for the method to be applicable in animal physiology and clinical toxicology.     

Analytical use of neutron-capture gamma-rays

Certain elements which are not possible to detect with conventional neutron activation analysis can be measured using thermal neutron-capture gamma-ray analysis. The use of a curved neutron guide at the High Flux Reactor, Grenoble, with a thermal neutron flux of 1.5·10¹⁰n·cm⁻²·sec⁻¹ and the advantage of a low-background counting system (Ge(Li) detector) far from the reactor core are described. Experimental detection limits of a number of elements are given for the low-energy and the high-energy regions. Some applications of the capture gamma-ray method in the whole energy range are studied and are briefly discussed.     

The determination of rare earth alloying additives in special steels by neutron activation analysis

A procedure for neutron-activation analysis of cerium, lanthanum, praseodymium and neodymium, tested on more than thirty samples of steels, is described. After irradiation for 20 hrs with a neutron flux of 1.2·10¹³ n·cm⁻²·sec⁻¹ the steel samples were dissolved in aqua regia and extraction separation of iron from 6N HCl by ether was employed. The REE were separated as a group by precipitation as fluorides and hydroxydes. The individual rare-earth elements were separated from each other using a KU-2 cation exchange resin and a solution of ammonium α-hydroxyisobutirate as eluant. The separated samples were counted on a NaI(T1) γ-spectrometer.     

Biosorptive behavior of mango (<Emphasis Type="Italic">Mangifera indica</Emphasis>) and neem (<Emphasis Type="Italic">Azadirachta indica</Emphasis>) barks for <Superscript>134</Superscript>Cs from aqueous solutions: A radiotracer study

The role of dead biomasses viz., mango (Mangifera indica) and neem (Azadirachta indica) bark samples are assessed in the removal behavior of, one of important fission fragments, Cs(I) from aqueous solutions employing a radiotracer technique. The batch type studies were carried out to obtain various physico-chemical data. It is to be noted that the increase in sorptive concentration (from 1.0·10⁻⁸ to 1.0·10⁻² mol·dm⁻³), temperature (from 298 to 328 K) and pH (2.6 to 10.3) apparently favor the uptake of Cs(I) by these two bark samples. The concentration dependence data obeyed Freundlich adsorption isotherm and the uptake follows first order rate law. Thermodynamic data evaluation and desorption experiments reveal the adsorption to be irreversible and endothermic in nature proceeding through ion-exchange and surface complexation for both dead biomasses. Both bark samples showed a fairly good radiation stability in respect of adsorption uptake of Cs(I) when irradiated with a 300 mCi (Ra-Be) neutron source having an integral neutron flux of ∼3.85·10⁶ n·cm⁻²·s⁻¹ and associated with a nominal γ-dose of ∼1.72 Gy·h⁻¹.     

<Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-Butylcalix[8]arene loaded silica gel for preconcentration of uranium(VI) via solid phase extraction

This paper reports silica gel loaded with p-tert-butylcalix[8]arene as a new solid phase extractor for determination of trace level of uranium. Effective extraction conditions were optimized in column methods prior to determination by spectrophotometry using arsenazo(III). The results showed that U(VI) ions can be sorbed at pH 6 in a mini-column and quantitative recovery of U(VI) (>95–98%) was achieved by stripping 0.4 mol L⁻¹ HCl. The sorption capacity of the functionalized sorbent is 0.072 mmol uranium(VI) g⁻¹ modified silica gel. The relative standard deviation and detection limit were 1.2% (n = 10) for 1 μg uranium(VI) mL⁻¹ solution and 0.038 μg L⁻¹, respectively. The method was employed to the preconcentration of U(VI) ions from spiked ground water samples.     

Measurement of alpha-decay constant to fission cross section ratio for actinides using solid state nuclear track detectors

A simple technique based on the measurement of the ratio of alpha-decay constant to neutron induced fission cross section for pure actinides using solid state nuclear track detectors (SSNTDs) is developed for the identification of the actinides in trace levels in pure solutions. The alpha-decay constant to fission cross section ratios for depleted U,²³⁸Pu and²⁴⁰Pu have been measured for the epicadmium neutron induced fission of these actinides. The measured values are (6.19±0.34)·10⁶, (6.95±0.26)·10¹², (2.12±0.95)·10⁹ and (2.18±1.58)·10¹¹ sec⁻¹·cm⁻², respectively. These ratios can be used for the trace level identification of pure actinides.     

Multi-element analysis of biological samples after intense neutron irradiation an fast chemical separation

For the simultaneous determination of many elements in small biological samples, a multi-element analysis has been developed using neutron activation. After a 24-hr irradiation in a neutron flux of 2.5·10¹⁴ n·cm⁻²·sec⁻¹ and after immediate chemical separation without cooling, it was possible to analyse 24 elements in bovine liver (NBS-SRM 1577). The separation apparatus, set up in a shielded cell can work four samples simultaneously, and its operation is fast enough to allow the detection of radioisotopes with a half-life of about 2 hrs (¹⁶⁵Dy,^57mSr,⁵⁶Mn). Amounts lower than 10⁻³ μg of Dy, Eu, Pr, Sm and Yb were determined.