<Superscript>3</Superscript>H and <Superscript>90</Superscript>Sr in urine radiobioassay intercomparison results from the intercomparison studies program at Oak Ridge National Laboratory: statistical analysis of laboratory performance

The Intercomparison Studies Program (ISP) at the Oak Ridge National Laboratory (ORNL, Oak Ridge, TN USA) provides natural-matrix human urine quality-assurance/quality-control (QA/QC) samples to radiobioassay analysis laboratories. Samples are provided to these laboratories as “single-blind” or “double-blind” unknowns, spiked with radioactive-solution standards at “low” levels (e.g., 0.7–7 Bq g⁻¹ for ³H and 0.7–7 Bq kg⁻¹ for ⁹⁰Sr). Participants use the results as a tool for self-evaluation and a measure of performance. In this paper, sample preparation and the results of testing during the years 2001–2005 for ³H and ⁹⁰Sr are presented and discussed.     

Using low resolution gamma detectors to detect and differentiate 239Pu and 235U fissions

When ²³⁹Pu and ²³⁵U undergo thermal neutron-induced fission, both produce significant numbers of beta-delayed gamma rays with energies in the several megaelectron volt range. Experiments using high energy-resolution germanium detectors have shown that it is possible to distinguish the fission of ²³⁹Pu from that of ²³⁵U. It is desirable to detect the presence of ²³⁵U or ²³⁹Pu using detectors that are less expensive and more rugged than high purity germanium detectors. To this end we demonstrate how differences in the energy spectrum and decay rates of the beta-delayed gamma rays can be used to identify ²³⁹Pu and ²³⁵U using low resolution plastic and liquid scintillator detectors. Experimental data are used to identify differences in the spectra and also to test the identification algorithms. Results to date are very promising.     

First results studying the transmutation of 129I, 237Np, 238Pu, and 239Pu in the irradiation of an extended natU/Pb-assembly with 2.52 GeV deuterons

An extended U/Pb-assembly was irradiated with an extracted beam of 2.52 GeV deuterons from the Nuclotron accelerator of the Laboratory of High Energies within the JINR in Dubna, Russia. The lay-out of this experiment and first results are reported. The Pb-target (diameter 8.4 cm, length 45.6 cm) is surrounded by a ^natU-blanket (206.4 kg) and used for transmutation studies of hermetically sealed radioactive samples of ¹²⁹I, ²³⁷Np, ²³⁸Pu and ²³⁹Pu. Estimates of transmutation rates were obtained as result of measurements of gamma-activities of the samples. Information about the spatial and energy distribution of neutrons in the volume of the lead target and the uranium blanket was obtained with sets of activation threshold detectors (Al, Y and Au) and solid state nuclear track detectors (SSNTD). An electronic ³He neutron detector was tested on-line. A comparison of experimental data with theoretical model calculations using the MCNPX program was performed yielding satisfactory results. Collaboration “Energy plus Transmutation” This work is dedicated to the cherished memory of Professor Vladimir Pavlovich Perelygin from the JINR in Dubna, Russia.     

Migration of239Pu in soluble and insoluble forms in soil

A field experiment study was performed at the rural site of South-East Lithuania. The main tasks of the study included an evaluation of the peculiarities of partition of²³⁹Pu in soluble (²³⁹Pu(NO₃)₄,²³⁹PuCl₃) and insoluble (²³⁹PuO₂) forms in soddy and forest soil horizons. The results of durable experiments (418 and 326 days) have shown that from 44.1% to 92.2% of²³⁹Pu of investigated chemical forms were accumulated in the top (0–5 cm) soil layer. Some share (5.7–39.2%) of plutonium from studied chemical forms was found in the 5–20 cm layers of studied soil samples (columns). Obtained distribution of plutonium in soil layers may be attributed to the consideration that the migration rate to the soil depth for plutonium is 0.1–1.0 cm·y⁻¹ but for some part of plutonium 10 times higher migration rate is characteristic as well. Plutonium transfer factor (TF) to the grassland plants was calculated, the values ranged from 10⁻² to 10⁻¹.     

A direct determination of 239Pu in femtomole range in aquatic solution by neutron activation

Summary A method is presented which facilitates the direct determination of ²³⁹Pu in aquatic solution by the (n,f) reaction with reactor neutrons and subsequent gamma spectrometry without chemical elaboration. Trace impurities of water constituent heavy metal elements are simultaneously determined through their (n, ) reactions. The sensitivity attained by this method is 1.6×10^–15 mol/l ²³⁹Pu by measuring the fission product pairs ¹³²Te/¹³²I or ¹⁴⁰Ba/¹⁴⁰La. The trace impurities determined in the range of 10^–810^–13 mol/l give an insight into the chemical behaviour of Pu in a given water. The natural uranium concentration plays a role to limit the Pu determination on the one hand and to help understanding the chemical behaviour of Pu on the other hand.

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Direkte Bestimmung von ²³⁹Pu in wäßriger Lösung im Femtomol-Bereich mit Hilfe der Neutronenaktivierung

Zusammenfassung Es wird eine Methode vorgestellt, die die direkte Bestimmung von ²³⁹Pu in wäßriger Lösung über die (n,f)-Reaktion mit Reaktorneutronen und mit anschließender gammaspektrometrischer Messung ohne chemische Aufbereitung ermöglicht. Spurenverunreinigungen der im Wasser enthaltenen Schwermetallelemente werden gleichzeitig über ihre (n, )-Reaktionen erfaßt. Durch die Messung der Spaltproduktpaare ¹³²Te/¹³²I oder ¹⁴⁰Ba/¹⁴⁰La wird bei dieser Methode eine Nachweisgrenze von 1,6×10^–15 mol/l ²³⁹Pu erreicht. Die bestimmten Spurenverunreinigungen im Bereich von 10^–8 bis 10^–13 mol/l geben einen Einblick in das chemische Verhalten von Pu in einem vorliegenden Wasser. Der natürliche Urangehalt spielt auf der einen Seite eine einschränkende Rolle bei der Pu-Bestimmung, trägt aber auf der anderen Seite zum Verständnis des chemischen Verhaltens von Pu bei.

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Dedicated to Prof. Dr. K. H. Lieser on the occasion of his 65th birthday     

Experimental Determination of the Isotherm at 15°C of the System Mg2+/Cl?, SO42–H2O

 The diagram of the ternary system Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O was established at 15°C by means of analytical and conductimetric measurements. Three compounds were found in this diagram, which are MgSO₄·6H₂O, MgSO₄·7H₂O, and MgCl₂·6H₂O. The solubility field of MgSO₄·7H₂O is important whereas those of MgSO₄·6H₂O and MgCl₂·6H₂O are small. The compositions (mass-%) of the two invariant points determined by the two methods are: MgSO₄:MgCl₂=2.73:33.80 and MgSO₄: MgCl₂=3.38:28.91. Both the measured and the calculated isotherm at 15°C have been used for modelling of the diagram Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O between 0 and 35°C. The polythermal invariant point was approximately located between 15 and 10°C.     

Molecular and crystal structure of 1-hydroxy-2-methyl-11-methylene-tricyclo (5.3.1.0)2,7-undecan-5-one, C13O2H18

The title compound is orthorhombic witha = 26·132(6),b = 11·023(2),c = 8·317(5), ?; space group Iba2;Z = 8,D _m = 1·21(1),D _c = 1·192 Mg m⁻³, 1/2(H₂O) per molecule in asymmetric unit; λ (MoKα) = 0·7107A; μ = 0·46 cm⁻¹; F(000) = 936. The structure was solved by direct methods and refined to R(F) value of 0·069 using 327 reflections withF ≥ 5σ(F) out of 727 independent reflections for2τ max = 46°. Thetrans fused cyclohexane and cyclohexanone rings form layers along thea-b plane. The axial methyl attached at the bridge-head, interlocks with the translated methylene of the cyclobutane fused across the cyclohexane ring. The equatorial hydroxyl at the bridge-head adjacent to the methyl junction and the water molecule on the two-fold form a water bridge along thez axis. The packing is reminiscent of that observed for the cholesterols used in membrane structure studies.     

Sorption and desorption of 125I-, 137Cs+, 85Sr2+ and 152,154Eu3+ on disturbed soils under dynamic flow and static batch conditions

Sorption of radionuclides on homogenized soils (under 2.5 mm grain size) from synthetic groundwater of 8·10⁻³M ionic strength and pH 8.5 has been studied under dynamic (flow) and static (batch) conditions. The corresponding water-soluble compounds, as carriers in the 10⁻⁶ mol/dm³ concentration, were added into the SGW prior to the experiments. Soil samples were taken from several locations around the environment of the High Level Waste Storage Facility at Nuclear Research Institute Řež plc in 5–100 cm depth. The dynamic experiments were carried out in columns made of PP+PE injection syringes of 17.8 cm length and 2.1 cm in diameter. A multi-head peristaltic pump was used for pumping the water upward through the columns at a seepage velocity of about 0.06 cm/min in average. The radioactive nuclides were added into the water stream individually in a form of a short pulse in 0.1 cm³ of demineralized water. Dynamic desorption experiments were performed with the same experimental arrangement using a mixture of 10⁻²N H₂SO₄ and 10⁻²N HNO₃ in a volume ratio of 2: 1. Retardation, distribution and hydrodynamic dispersion coefficients during transport of radionuclides were determined by the evaluation of the integral form of a simple advection-dispersion equation, used for fitting experimental data and modeling the theoretical sorption breakthrough and desorption displacement curves. The static experiments were realized in 100 cm³ plastic bottles stirring 5 g of soil samples with SGW occasionally in a soil to SGW ratio of 1: 10 (m/V). Kinetic parameters including equilibrium sorption activity, activity transfer rate constants and sorption half-times were also determined. The results of dynamic experiments were compared with static sorption experiments.     

<Superscript>239, 240, 241</Superscript>Pu fingerprinting of plutonium in western US soils using ICPMS: solution and laser ablation measurements

Sector field inductively coupled plasma mass spectrometry (SF-ICPMS) has been used with analysis of solution samples and laser ablation (LA) of electrodeposited alpha sources to characterize plutonium activities and atom ratios prevalent in the western USA. A large set of surface soils and attic dusts were previously collected from many locations in the states of Nevada, Utah, Arizona, and Colorado; specific samples were analyzed herein to characterize the relative contributions of stratospheric fallout vs. Nevada Test Site (NTS) plutonium. This study illustrates two different ICPMS-based analytical strategies that are successful in fingerprinting Pu in environmental soils and dusts. Two specific datasets have been generated: (1) soils are leached with HNO₃-HCl, converted into electrodeposited alpha sources, counted by alpha spectrometry, then re-analyzed using laser ablation SF-ICPMS; (2) samples are completely dissolved by treatment with HNO₃-HF-H₃BO₃, Pu fractions are prepared by extraction chromatography, and analyzed by SF-ICPMS. Optimal laser ablation and ICPMS conditions were determined for the re-analysis of archived alpha spectrometry “planchette” sources. The best ablation results were obtained using a large spot size (200 μm), a defocused beam, full repetition rate (20 Hz) and scan rate (200 μm s⁻¹); LA-ICPMS data were collected with a rapid electrostatic sector scanning experiment. Less than 10% of the electroplated surface area is consumed in the LA-ICPMS analysis, which would allow for multiple re-analyses. Excellent agreement was found between ^239+240Pu activities determined by LA-ICPMS vs. activity results obtained by alpha spectrometry for the same samples ten years earlier. LA-ICPMS atom ratios for ²⁴⁰Pu/²³⁹Pu and ²⁴¹Pu/²³⁹Pu range from 0.038–0.132 and 0.00034–0.00168, respectively, and plot along a two-component mixing line (²⁴¹Pu/²³⁹Pu = 0.013 [²⁴⁰Pu/²³⁹Pu] – 0.0001; r ² = 0.971) with NTS and global fallout end-members. A rapid total dissolution procedure, followed by extraction chromatography and SF-ICPMS solution Pu analysis, generates excellent agreement with certified ^239+240Pu activities for standard reference materials NIST 4350b, NIST 4353, NIST 4357, and IAEA 385. ^239+240Pu activities and atom ratios determined by total dissolution reveal isotopic information in agreement with the LA-ICPMS dataset regarding the ubiquitous mixing of NTS and stratospheric fallout Pu sources in the regional environment. For several specific samples, the total dissolution method reveals that Pu is incompletely recovered by simpler HNO₃-HCl leaching procedures, since some of the Pu originating from the NTS is contained in refractory siliceous particles.     

Measurement of the radioactivity of 238U, 226Ra, 210Pb, 228Th, 232Th, 228Ra, 137Cs and 40K in tea using gamma-spectrometry

The aim of the present work was to determine the concentration of radionuclides in all kinds of tea available at the local Egyptian market. Radioactivity of the nuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²²⁸Th, ²³²Th, ²²⁶Ra, ¹³⁷Cs and ⁴⁰K were measured in tea by direct γ-ray spectrometry using HPGe detector and their mean values were 16.0±5.3, 3.1±0.7, 34.3±3.4, 3.4±1.2, 3.0±0.6, 3.1±0.8, 0.9±0.2 and 623±25 Bq·kg⁻¹, respectively.     

137Cs, 40K, 90Sr, 238, 239+240Pu, 241Am and 243+244Cm in forest litter and their transfer to some species of insects and plants in boreal forests: Three case studies

Results for ¹³⁷Cs, ⁴⁰K, ⁹⁰Sr, ^238,239+240Pu, ²⁴¹Am and ^243+244Cm measurements in plant, insects and forest litter samples collected at three sites in Poland are presented. New results are compared with some existing data for locations examined during previous studies. Insect samples were introduced now for the first time. Relatively high activities of ⁹⁰Sr were noticed for spruce bark beetle (Ips typographus) and those for ¹³⁷Cs, plutonium and ²⁴¹Am for forest dung beetle (Anoplotrupes stercorosus). Faster than caused by physical decay decrease of radiocesium activity was noticed for the majority of plant and litter samples. The results for ^239+240Pu for litter were similar to previous results, but the activities of ²³⁸Pu were smaller. The activity ratio between ²⁴¹Am and ^239+240Pu was found lower than expected for known proportions between global and Chernobyl fallout. Thus a kind of dynamic behavior of Pu and Am in the forest ecosystem is concluded. Transfer factors and aggregation coefficients were estimated and discussed for both plants and insects as well as between insects and the part of plants (or litter) they feed on. Many of them were never presented before.The authors are thankful to the Polish State Committee for Scientific Research for financial support of this investigation, Grant No. PG04 07520.     

Pu isotopes and137Cs in the surrounding areas of the former Soviet Union's Semipalatinsk nuclear test site

Field missions were sent to Semipalatinsk City and several settlements near the former Semipalatinsk nuclear test site to investigate the current radioactive contamination levels of the land coming from long-lived radionuclides. The soil was sampled at about 20 sites, including some settlements such as Mostik, Dolon and Chagan, forest and pasture areas, along the roads from Semipalatinsk City to Kurchatov City and to Korosteli settlement in the direction of the Altai District. The radioactivities of¹³⁷Cs,²³⁸Pu and^239,240Pu as well as²⁴⁰Pu/²³⁹Pu atomic ratios in the soil were determined by non-destructive γ-ray spectrometry and radiochemical separation followed by α-ray spectrometry and/or ICP-MS, respectively. The results showed a distinction of¹³⁷Cs and^239,240Pu inventories in soil depending on the site where we visited. While the overall¹³⁷Cs levels were as same as or slightly lower than the domestic global fallout level (3·10³–7·10³ Bq/m²),^239,240Pu levels at some sites were several to a few ten times higher than the domestic level (40–120 Bq/m²). The atomic ratios of²⁴⁰Pu/²³⁹Pu in the soil were in the range of 0.024–0.125, which were significantly lower than the value of 0.18 commonly accepted for global fallout Pu.     

Determination of total and extractable hydrogen peroxide in organic and aqueous solutions of uranyl nitrate

The development of a spectrophotometric method for the determination of hydrogen peroxide in uranyl nitrate solutions is reported. The method involves the measurement of the absorbance at 520 nm of a vanadyl peroxide species. This species was formed by the addition of a reagent consisting of vanadium (V) (50 mmol·dm⁻³) in dilute sulphuric acid (2 mol·dm⁻³ H₂SO₄). This reagent, after dilution, was also used as an extractant for organic phase samples. The method is simple and robust and tolerant of nitric acid and U(VI). Specificity and accuracy were improved by the application of solid phase extraction techniques to remove entrained organic solvents and Pu(IV). Reverse phase solid phase extraction was used to clean-up aqueous samples or extracts which were contaminated with entrained solvent. A solid phase extraction system based upon an extraction chromatography system was used to remove Pu(IV). Detection limits of 26 μmol·dm⁻³ (0.88 μg·cm⁻³) or 7 μmol·dm⁻³ (0.24 μg·cm⁻³) for, respectively, a 1 and 4 cm path length cell were obtained. Precisions of RSD=1.4% and 19.5% were obtained at the extremes of the calibration curve (5 mmol·dm⁻³ and 50 μmol·dm⁻³ H₂O₂, 1 cm cell). The introduction of the extraction and clean-up stages had a negligible effect upon the precision of the determination. The stability of an organic phase sample was tested and no loss of analyte could be discerned over a period of at least 5 days. The presence of trace levels of reductants interfered with the determination, e.g., hydrazine (<2 mmol·dm⁻³), but this effect was ameliorated by increasing the concentration of the colormetric reagent.     

Improved sample preparation method for environmental plutonium analysis by ICP-SFMS and alpha-spectrometry

A rapid and simple sample preparation method for plutonium determination in environmental samples by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) and alpha-spectrometry is described. The developed procedure involves a selective CaF₂ co-precipitation for preconcentration followed by extraction chromatographic separation. The proposed method effectively eliminates the possible interferences in mass spectrometric analysis and also removes interfering radionuclides that may disturb alpha-spectrometric measurement. For ²³⁹Pu, ²⁴⁰Pu and ²⁴¹Pu limits of detection of 9.0 fg·g⁻¹ (0.021 mBq), 1.7 fg·g⁻¹ (0.014 mBq) and 3.1 fg·g⁻¹ (11.9 mBq) were achieved by ICP-SFMS, respectively, and 0.02 mBq by alpha-spectrometry. Results of certified reference materials agreed well with the recommended values.     

Determination of plutonium by solvent extraction—Liquid scintillation method

A combined solvent extraction—liquid scintillation method is suggested for the determination of plutonium. The quenching by twenty four extracting reagents was examined systematically, and the organo phosphorus extractants such as tributylphosphate (TBP), bis-(2-ethyhexyl) phosphoric acid (HDEHP), and tri-n-octylphosphineoxide (TOPO) were shown to be least quenching compared with amines and beta-diketones. Using TOPO, plutonium from 1 ng to 2 μg was determined within 5% of standard deviation, and the detection limit was 3·10⁻¹⁰ g of²³⁹Pu. The quenching by the different ions and the effects of the radioactive elements were also shown.     

Use of ultrathin zirconium phosphate layers for the preparation of alpha-spectrometric samples

Ultrathin zirconium phosphate layers about 300–600 nm in thickness have been prepared on stainless steel supports. The adherence and homogeneity of the layers are sufficient. The adsorption properies in respect to alpha-emitters (²³⁹Pu and²⁴¹Am) have been studied. The adsorption equilibrium is reached in half an hour and a total capacity of about 3–4 μg Pu has been estimated. Alpha-spectrometric properties of the samples have been evaluated by measuring the half-width of the²³⁹Pu main peak, which is close to the resolution ability of the detector.     

Evaluation of 239+240Pu, 137Cs and natural 210Pb fallout in agricultural upland fields in Rokkasho, Japan

The background distributions of ^239+240Pu and ¹³⁷Cs fallout in agricultural soil were investigated in Rokkasho where Japan's first commercial nuclear fuel reprocessing plant is now being constructed. The mean inventories of ^239+240Pu and ¹³⁷Cs in three fields with non-yam-cultivation history were 116 Bq·m⁻² and 3.4 kBq·m⁻², respectively. The mean atomic ratio of ²⁴⁰Pu/²³⁹Pu for all studied fields was 0.18±0.04, and was similar to that of global fallout. The ^239+240Pu concentrations correlated very well with ¹³⁷Cs (r = 0.97) in spite of heavy disturbance of the soil, and the activity ratio of ^239+240Pu/¹³⁷Cs was 0.037±0.007, which is a typical value for global fallout. These results showed that the nuclides had similar behavior in agricultural upland fields in Rokkasho. Since ²¹⁰Pb is steadily deposited from the atmosphere to the land, this nuclide could be an index for the degree of disturbance of a field and of soil lost from the field. The ratio of excess ²¹⁰Pb inventory in the soil to the equivalent inventory of atmospheric ²¹⁰Pb deposition was 96%, and indicated that soil was not lost from the cultivated fields. This revised version was published online in July 2006 with corrections to the Cover Date.     

Differential pulse polarographic study of thiamine (vitamin B1) in neutral and acidic aqueous solutions

The differential pulse (dp) polarograms of thiamine in neutral aqueous solutions exhibited six peaks at low depolarizer concentration (⋦10⁻⁴ mol dm⁻³) and only three peaks at concentrations ≥10⁻³ mol dm⁻³. Only one of these was found to correspond to the diffusion-controlled reduction of this compound at the dme and this was shown to be an irreversible two-electron process. The kinetic parameters derived from the dp polarograms were found to be in good agreement with those calculated from classical polarograms and were:E _1/2=−1·261 Vvs SCE,an _a=0·54 andD≈3·5×10⁻⁶ cm² sec⁻¹ for 10⁻³ mol dm⁻³ thiamine in 0·1 mol dm⁻³ acetate buffer (pH 6·5). The reduction product has been identified as dihydrothiamine. The effect of pH on the dpp of thiamine was studied in the pH range 0–7. In the pH region 5·5 to 7·0 only one peak attributable to the B₁ ⁺ form of thiamine is present. In the pH region 3·5–5·5 another dpp peak attributable to the protonated form (B₁H²⁺) of thiamine was also observed. At pHs less than 3 only one peak was observed which could be attributed to the doubly protonated form (B₁ H₂ ³⁺) of thiamine. Surfactants like triton-X-100 and CTABr were found to inhibit the electroreduction of thiamine due to the strong adsorption of these compounds on the dme. Thiamine itself was found to have an inhibitory effect on its own electroreduction, although to a smaller extent.     

Synthesis and Crystal Structure of Cucurbit[6]uril Adduct of Hydrogen-bonded Cluster Complex [Mo3(μ3-Se)(μ2-O)3(H2O)6Cl3]+

Reaction of [MoOCl₅]²⁻ with in situ generated H₂Se under hydrothermal conditions (4M HCl, 140 °C) leads to reduction of Mo(V) to Mo(IV) with the formation of a triangular cluster Mo₃(μ₃-Se)(μ-O)₃⁴⁺ in high yield. It is present in HCl solutions as aqua chlorocomplex [Mo₃(μ₃-Se)(μ-O)₃(H₂O)₆Cl₃]⁺ which was isolated and structurally characterized as supramolecular adduct with cucurbit[6]uril (CB[6]), {[Mo₃(μ₃-Se)(μ-O)₃(H₂O)₆Cl₃]₂CB[6]}Cl₂·15H₂O. Dedicated to Professor Dieter Fenske on the Occasion of his 65th Birthday     

Plutonium process control using an on-line gamma monitor for uranium,plutonium, and Americium

An On-Line Gamma Monitor profiles the concentration of uranium, plutonium, and americium in waste and product streams of the anion exchange process used to purify plutonium at Los Alamos. The Monitor employs passive gamma Spectrometry to measure the 59.5-KeV and 129-KeV gamma rays of²⁴¹Am and²³⁹Pu, respectively. Because the uranium impurity in typical process streams has no gamma ray suitable for passive measurement, a novel radiotracer technique is used. Uranium-237, always present in plutonium processed at Los Alamos as a minor alpha-decay daughter of²⁴¹Pu, has a 6.8-day half-life and 208-KeV gamma energy, which make it an ideal radiotracer for macro amounts of uranium in the process. The On-Line Gamma Monitor is used routinely to provide Los Alamos operators with continuous, real-time process control information.