A gamma-spectrometric method for the determination of plutonium isotope ratios

A gamma-spectrometric method using an intrinsic high resolution germanium detector has been developed for the determination of isotope ratios of plutonium from samples in solution form. The method is based on the assay of low energy gamma-rays of²³⁸Pu,²³⁹Pu,²⁴⁰Pu and²⁴¹Pu and does not require the use of branching intensities or the knowledge of detection efficiencies for different gamma rays. Since low energy gamma-rays are used, the effect of²⁴¹Am has also been studied. It is found that results are not affected up to 0.5 wt% of²⁴¹Am in plutonium samples. An accuracy of 3% is achievable in the determination of²⁴⁰Pu/²³⁹Pu and²⁴¹Pu/²³⁹Pu atom ratios as demonstrated by carrying out measurements on isotopic standards of plutonium.     

A spectrophotometric method for the determination of plutonium in fuel solutions

A spectrophotometric method is described in which microgram amounts of plutonium can be determined in the presence of uranium, thorium, fission products and cladding materials. Plutonium is extracted with TTA in xylene and reextracted into a solution of Arsenazo III. Zirconium is masked by a Fe(III)-EDTA mixture, fluoride ions by Al(III). 2 to 40 μg of plutonium are required for one analysis. The standard deviation is 1.3% at 15 μg plutonium.     

A routine method for the determination of retronecine

A method for the routine determination of the necine base retronecine from biological matrices is described, using gas chromatography for quantification. The biological matrices studied included blended sheep whole rumen fluid and bacterial growth media. The structurally similar compound 2,6-dimethoxypyridine was utilized as an internal standard. Prior to gas chromatography, the bis(heptafluorobutyrate) derivatives of both compounds were formed. The relative percent recoveries of retronecine and the internal standard were 73% and 82%, respectively. The detection limit of retronecine in blended whole rumen fluid was found to be 0.09 μg/mL, and 0.02 μg/mL in bacterial growth media. The precision of the peak area ratio (retronecine to internal standard) was 10% from blended whole rumen fluid, and 14% from bacterial growth media. This method was used to analyze samples from viable cultures incubated with retronecine. Received: 6 May 1997 / Revised: 29 September 1997 / Accepted: 2 October 1997     

A titrimetric method for the sequential determination of thorium and plutonium

A method for the sequential determination of thorium and plutonium has been developed. In the sample solution containing thorium and plutonium, thorium is first determined by complexometric titration with EDTA and then in the same solution plutonium is determined by redox titration employing potentiometry. Prior to the determination of plutonium, EDTA is destroyed by fuming with concentrated HClO₄. Thorium is determined at 10 mg level and plutonium at 1 mg level with precision and accuracy of better than ±0.5%.     

A modified radiometric method for plutonium determination in irradiated fuel

A modified radiometric method for the determination of plutonium in irradiated nuclear fuel is described. The analysis consists of total plutonium alpha-activity, activity ratio²³⁸Pu:(²³⁹Pu+²⁴⁰Pu) and burnup determination. The error of plutonium determination is practically identical with that of a classical radiometric method. The method suggested is suitable for large sample series of the same type of irradiated nuclear fuel.     

Modified TTA method for the determination of plutonium

The spent fuel from Fast Breeder Test Reactor of various burnups from 25 to 155?GWd/te is being reprocessed in CORAL (COmpact Reprocessing of Advanced fuels in Lead shielded cell) using a modified PUREX (Plutonium Uranium Recovery by EXtraction) process. Total plutonium (Pu^{238, 239, 240, 241 & 242}) concentration in the sample is analysed by HTTA (Thenoyl Trifluoro Acetone) extraction method wherever interference from other alpha emitting nuclides (Raffinate) and bulk natural uranium (uranium products) are present "as reported by Milyukov et al. (Analytical chemistry of plutonium, 1967) and Natarajan and Subba Rao (BARC, pp. 38?C43, 2007)". This method requires the addition of corrosive reagents such as NH₂OH.HCl which is a problem in waste disposal for reduction. A salt-free reagent such as Hydroxyurea is studied as a reducing agent which has the ability to reduce both Pu(VI) and Pu(IV) to Pu(III) "as reported by Zhaowu (260(3):601?C606, 2004) and Zhaowu (262(3):707?C711, 2004)". Pu(III) thus formed can be easily oxidised to Pu(IV) by NaNO₂ for the extraction of Pu by HTTA.     

A chloroquine membrane electrode with low detection limit

A PVC membrane electrode for chloroquine [7-chloro-4-(4-diethylamine-1-methylbutylamino)-quinoline] based on a chloroquine/dinonylnaphthalene sulphonic acid ion-pair is described. The electrode shows near-Nernstian response in the 10^?2–10^?6 M range and a detection limit of 2 × 10^?7 M. Its selectivity relative to various inorganic ions, amino acids, neurotransmitters, drugs, and some excipients is reported. Direct potentiometry is used to determine chloroquine in pharmaceutical preparations with good results.     

Comparison of a novel thin-layer chromatographic-fluorescence detection method with a spectrofluorometric method for the determination of 7-hydroxycoumarin in human urine.

A novel method for the determination of 7-hydroxycoumarin in human urine which combines thin-layer chromatography (TLC) with fluorescence detection (FD) has been devised. The limit of detection (1 ng/ml) enables determination of 7-hydroxycoumarin after both administration of coumarin and environmental exposure to this fragrance material. When compared to a spectrofluorometric method of analysis, the TLC-FD method proved to be more selective for the analysis of 7-hydroxycoumarin in human urine.     

A spectrophotometric method for the determination of neptunium and plutonium in process solutions

A method is described for the determination of neptunium and plutonium in process solutions. This involves the separation of these elements followed by their spectrophotometric determination as Arsenazo III complexes. Neptunium(IV) and plutonium(IV) are separated using TTA extraction method and the separated Np(IV) and Pu(IV) are then determined as their Arzenazo III complexes in 5M HNO₃. A few solutions obtained by dissolving irradiated fuels were analysed for plutonium and neptunium using this method and the results were compared with those obtained by other methods. An attempt was made to use Arsenazo III to determine uranium in the plant solutions.     

A fast method for the determination of plutonium in soil and sediment samples

A so-called hour method for the determination of plutonium based on extraction chromatography is validated by its application to several certified soil and sediment samples from the International Atomic Energy Agency's Seibersdorf Laboratory. The results are in good agreement with the reference values. Chemical yields range between 47%–66%, with a mean value of (56±6)%. The possible use of this method for²⁴¹Pu determination is also demonstrated.     

A sensitive method for the determination of tritium in urine

An analytical procedure was developed for the determination of tritium in urine. The content of contaminants in urine after treatment is reduced markedly so that no influence is expected on tritium measurements by a liquid scintillation counter. The established analytical procedure was successfully applied for urine from the general public in Japan.     

A cleanup method for perchlorate determination in urine

There is increasing concern about perchlorate exposure because of perchlorate's potential effects on organisms as a thyroid hormone disruptor, as well as its contamination of the environment being much more widespread than previously thought. Perchlorate is excreted primarily into urine, therefore, evaluating perchlorate residues in urine should be a reasonable approach for determining exposure and if successful could be used as an effective biomarker of perchlorate exposure. Since the presence of ions and other biomolecules in matrices like urine usually confounds accurate determination of perchlorate by ion chromatography, it is necessary to develop efficient methods for perchlorate determination in these matrices. We developed a method that reduces the background signal of urine, which is typically the problem with the analysis of biological fluids and tissues by ion chromatography. Relatively high recovery of perchlorate was shown. In cow urine samples spiked with perchlorate at 2.5, 10, and 100 μg/L, perchlorate recoveries were 67% ± 2.5, 77% ± 3.6, and 81% ± 1.7 (mean ± S.D.), respectively. In addition, the detection limit was as low as 12.6, 12.3, and 18.7 μg/L in cow, vole, and human urine samples, respectively.     

Improved method for the constant-current potentiometric determination of plutonium

A highly precise method is described for the determination of plutonium by constant-current potentiometric titration with primary standard potassium dichromate. The relative standard deviation is 0.04% or better.     

A simple potentiometric method for the determination of reducing substances in urine with a copper-selective electrode

A potentiometric method for the determination of reducing substances in urine is described. Samples are treated with Stanley—Benedict reagent and the unused copper(II) is determined with a copper(II)-selective electrode by the standard addition technique. Glucose in the range 25–200 μg in 0.1ml samples can be determined with an average error of about 2%. The recovery of added glucose for six samples was 96–107% (average 100.5%). Comparison with the conventional titrimetric method shows good agreement. The effect of other non-glucose reducing substances present in urine is reported.