PU and NP analysis of soil and sediment samples with ICP-MS

A method to analyse Pu and Np was optimised to achieve low detection limits and high sample throughput. Soil and sediment samples were ashed and digested with a borate fusion. After dissolving the melt in nitric acid, Pu and Np were separated on a TEVA extraction chromatopraphy column. It was measured with a sector field ICP-MS. Detection limits in soils and sediments as low as 1×10⁻¹⁵ g/g for Pu and Np were achieved. The method was applied to reference materials, soil profiles from Switzerland and sediment samples from the river Yenisei (RU), where radioactive nuclides have been discharged.     

Micro-column solid phase extraction to determine uranium and thorium in environmental samples.

Extraction chromatographic separation techniques based on U/TEVA and TEVA resins were utilized to separate uranium and thorium isotopes in complex matrices from environmental samples. This approach has the advantages of ease of quantitative analysis, small sample size, an absence of mixed waste solvents, complete separation of U/Th isotopes, acceptable chemical yields and good energy resolution in the alpha spectrum. The procedure for analyzing alpha-emitting isotopes of uranium and thorium in geothermal water from Peito, Taiwan, is illustrated in detail. It involves sample pre-concentration, filtration and separation by highly selective extraction chromatographic resins, followed by electroplating and alpha-spectroscopy. The analytical results show a chemical recovery exceeding 55% for U and 65% for Th, respectively, under optimized conditions. The efficient and cost-effective use of recyclable columns makes the analytical methods simple, accurate, rapid, reliable and robust.     

Sequential determination of Pu and Am radioisotopes in environmental samples; a comparison of two separation procedures.

Two separation methods for the sequential determination of Am and Pu radionuclides are presented and the results obtained are compared. Analysis involves leaching the sample with concentrated nitric acid (HNO(3)), followed by radiochemical separation using extraction chromatographic resins (UTEVA, TRU) and anion exchange. Sources for alpha spectrometry were prepared by micro-precipitation on neodymium fluoride (NdF(3)). The chemical recoveries were determined using (242)Pu and (243)Am tracers. The methods were tested on reference materials and on two sediments. All the results were in good agreement with the reference values. The evaluation of uncertainty is also included.     

Determination of Np-237 by radiochemical neutron activation analysis combined with extraction chromatography.

A procedure for determination of 237Np, 238Pu, 239,240Pu and 241Pu in environmental samples is described. Neptunium-237 is determined using radiochemical neutron activation analysis with pre- and post-irradiation chemistry based on solvent extraction and extraction chromatography. 238Pu, 239,240Pu is determined using alpha spectrometry and 241Pu by liquid scintillation spectrometry. The vertical profiles of 237Np, 238Pu, 239,240Pu in bottom sediments from the Black Sea are presented.     

Reduction of carcinogenic chromium(vi) on the skin of living rats

The reduction of chromate (Cr(VI)) on the skin of living rats was investigated using the technique of in vivo electron paramagnetic resonance (EPR) spectroscopy with a surface coil resonator. Topical application of aqueous solution of Cr(VI) on the skin of rats generated the transient species, Cr(V). Partial removal of the stratum corneum increased the rates of formation and decay of Cr(V), as well as Cr(V) signal intensity. The results demonstrate that skin represents one route for chromium to enter into animals and humans. The generation of reactive Cr(V) species in the reduction of Cr(VI) by the skin may play an important role in the mechanism of Cr(VI)-induced skin cancer. These findings indicate the potential for in vivo EPR spectroscopy for studying the metabolism of paramagnetic reactive species in chemical and biochemical reactions occurring in/on the skin of both small and large animals, and possibly humans.     

X- and gamma-ray emissions observed in the decay of 237Np and 233Pa.

Solvent extraction was used to prepare pure solutions of (237)Np and (233)Pa. Portions were used for liquid scintillation counting (disintegration rates) and gamma-ray spectroscopy with HPGe detectors. X- and gamma-ray intensities observed in the (237)Np decay were verified, with a new result of 15.08+/-0.04% for the 29 keV gamma-ray (5 sigma higher than previous reports). K X- and gamma-ray intensities observed in the (233)Pa decay were verified with new results for the L X-ray intensities (approximately 55% total L intensity), approximately twice previously reported total intensity.     

Methylene blue-enhanced stability of (99mTc)HMPAO and simplified quality control--a comparative investigation.

(99mTc)HMPAO is a radiopharmaceutical used for SPECT imaging of regional cerebral perfusion and for labeling cellular blood elements. The addition of methylene blue enhanced the stability of lipophilic (99mTc)HMPAO complex up to 3 h after reconstitution, 86.9+/-4.2% compared to 49.8+/-8.9% for the non-stabilised complex and persists over time (86.2+/-3.5% after 15 min compared to 78.2+/-4.0% after 3 h). The method widely used for estimation of radiochemical purity is a standard chromatographic procedure which is quite time-consuming taking about 30 min. Comparison of the more rapid and simple solvent extraction method with octanol, which needs only about 10 min to complete. showed a good correlation with the chromatographic method (84.4+/-4.4% compared to 89.1+/-4.3%). Using ethyl acetate as solvent instead of octanol gave a slightly higher extraction rate of the lipophilic complex (91.5+/-5.5% compared to 89.1+/-4.3%). Further, the ethyl acetate extraction method results in an overestimation, extracting partly secondary complex. It is confirmed, that the stability of the lipophilic (99mTc)HMPAO complex can be increased with methylene blue. The octanol extraction method, using higher extraction volume (up to 3 ml), is recommended as a fast and efficient approach for the quality control in daily clinical routine.     

Identification of transferrin as the principal neptunium-binding protein in the blood serum of rats

The binding of 239Np(V) to blood serum components of rats was examined in vivo and in vitro. After gel filtration of the serum using a Sephacryl S-300 column, 98% of the applied activity appeared with protein fractions representing coeluted albumins and transferrin. A separation of the albumin- and transferrin-proteins by ion-exchange chromatography using DEAE-cellulose showed the 239Np being entirely bound to the iron-carrier protein transferrin. The high elution yields from the ion-exchange columns, greater than 90%, suggest that the binding may be quite strong. The binding capacity of transferrin for neptunium in vivo was found to decline when the iron level in blood serum was increased. Precipitation experiments showed that 84 +/- 2% of the 239Np was precipitated with 10% (w/v) trichloracetic acid, 77 +/- 3% with 90% ethanol but only 6 +/- 1% with saturated ammonium sulphate at pH 7.4. The available data indicate that as for plutonium, thorium, americium and curium, the iron transport protein, transferrin, may be the main carrier protein for neptunium in mammalian blood serum.     

Chromium(VI) as a novel MRI contrast agent for cerebral white matter: preliminary results in mouse brain in vivo.

This work demonstrates that intraventricular microinjections of a low dose of potassium dichromate (0.4 microL of 10 mM solution) yield a specific contrast enhancement of white matter (WM) tracts in T1-weighted 3D MRI of mouse brain in vivo. Pronounced and persistent signal increases (40-100% at 24 hr after injection) were observed in the corpus callosum, anterior commissure, fornix, and stria medullaris, as well as in the mammillothalamic tract and fasciculus retroflexus. These results suggest that the extracellular diffusion of diamagnetic chromium(VI) (Cr(VI)) after injection is followed by a tissue-specific reduction to paramagnetic Cr(V) and (III), which relies predominantly on the oxidation of myelin lipids. Because Cr(VI)-induced contrast leads to only a mild unspecific enhancement (10-20%) of gray matter (GM) structures, such as the hippocampal formation, the method reveals novel information that differs from that obtainable using other paramagnetic ions, such as manganese.     

Comparison of toxicity rankings of six aircraft cabin polymers by lethality and by incapacitation in rats.

Polymeric aircraft cabin materials have the potential to produce toxic gases in fires. Lethality (LC50) in animal models is a standard index to rank polymers on the basis of their combustion toxicity. However, the use of times-to-incapacitation (ti) may be more realistic for predicting relative escape times from a fire. Therefore, LC50 and ti for polymers, polyamide (I), polystyrene (II), Nylon 6/6 (III), polysulfone (IV), polyethylene (V) and chlorinated polyethylene (VI), of different chemical classes were determined and compared. Male rats, 12/fuel loading, were exposed to the pyrolysis products from selected weights of each polymer for 30 min in a 265-L combustion/exposure system, and LC50 values were determined following a 14-d observation period. For each polymer, ti was measured at 16 g and at its respective LC50 using the inability of rats (n greater than or equal to 12) to walk in rotating cages as a criterion for incapacitation. LC50 (45.7-87.5 mg/L) of the polymers had the order of I less than II approximately III less than IV less than V less than VI, while their ti (6.6-21.1 min) at 16 g (60 mg/L) had the order of III approximately I less than V approximately II less than VI less than IV. Based on ti at LC50, polymers were grouped into III & V; I, II & VI; and IV. LC50 and ti did not exhibit the same relative toxic hazard rankings for these polymers; ti were also not equal at the LC50 concentrations. These findings demonstrate the possible involvement of different mechanisms of action for the combustion products of these polymers at the selected end points.     

Simultaneous determination of 226Ra, 233U and 237Np by liquid scintillation spectrometry.

A method has been developed for the simultaneous determination of 226Ra, 233U and 237Np by liquid-scintillation (LS) spectrometry. This method consists of the evaluation of the alpha-spectrum that is composed of the strongly overlapping peaks of 226Ra, 233U, 237Np, 222Rn and 218Po in the energy range of 4.60-6.00 MeV and the single 214Po peak at 7.69 MeV. The alpha-peaks are analysed by a special peak fit function that considers the deviation of the alpha-peak at the low energy side from the pure Gaussian shape. First 237Np is determined using its daughter 233Pa by analysing the beta-spectrum in the range 150-570 keV. 226Ra follows from the alpha-spectrum that is measured 6 weeks after sample preparation, i.e., 226Ra is determined from the radioactive equilibrium with its short-lived daughters 222Rn, 218Po and 214Po. Finally the 233U activity results from the fitted spectrum in the range of 4.4-4.8 MeV by subtracting the activity of 226Ra and 237Np. Knowing the exact energy position of the LS-peaks an alternative evaluation consists in the accurate deconvolution of the first three peaks that are formed by 226Ra and 233U (maximum of both at channel 700), 237Np (maxima at channels 700 and 725) and 222Rn (maximum at channel 737). In these two ways 226Ra, 233U and 237Np can be determined in mutual activity ratios of 1:50 with a relative standard deviation of less than 4% for the major activity and 9% for the minor activity.     

Adsorption of Se species on crushed granite: a direct linkage with its internal iron-related minerals.

The adsorption of selenium species on crushed granite is investigated directly linking to its internal iron-related minerals. Experimental results demonstrated that granite has higher affinity toward Se(IV) adsorption than Se(VI) adsorption. Se(IV) adsorption on granite is insensitive to background electrolytes while the effect of ionic strength on Se(VI) adsorption is not observed, which is attributed to the overloading of Se(VI) ions. Results of chemical sequential extraction showed that the removal of crystalline iron oxides dramatically reduces Se(IV) adsorption, which corresponds to the disappearance of goethite signal within XRD pattern. Based on our results, it is proposed that goethite within granite dominates Se adsorption in crushed granite. Although these goethites probably stem from some sample preparation processes including drilling in situ, crushing, washing and drying granite samples in laboratory, the formation of goethite enhances the granite affinity toward Se species adsorption. Images of SEM/EDS furthermore revealed that goethite is embedded within the fractures. In addition, quantification by standard addition method by spiking goethite suspension indicates that only around 20% of goethite minerals are available during Se(IV) adsorption.     

Research and identification of tranquillizers - use of retention index.

At the request of the Service des Haras, our laboratory works on the toxicological problems of the sport-horse. These studies have resulted in the setting up of an anti-doping control for equestrian competitions of various types, not only flat racing. During events, horses, must be calm and docile to the riders' order. Frequently, the latter use tranquillizers to try and win events. The analytical method for the research and identification of these compounds is described. The technique involves successively: 1. alkalinisation of the sample - saliva, blood or urine after enzymatic hydrolysis. 2. extraction with diethyl ether - the recovery is 70% to 90% depending upon the drug. 3. determination by gas-liquid chromatography with use of a retention index for qualitative analysis. We can detect up to fifteen tranquillizers in any one sample, even when present at such low concentrations as found in saliva. The use of the retention index is a reliable method for qualitative analysis. For example, the method has been used for three years, during which period the rentention index of acetylpromazine remained at 3240 +/- 7. The chromatographic analysis was performed on 3% OV-17 at 290 degrees. The chromatographic analysis has been performed by three columns of different polarity (OV-1; OV-17; SP-2250). If on the three columns, the retention index of one peak is the same as that of the tranquilizer, a further confirmation is made with the use of a thermionic detector specific for nitrogenous drugs. In conclusion, this method which is sufficiently precise and specific has been used for anti-doping control.     

Accurate determination of 129I concentrations and 129I/137Cs ratios in spent nuclear resins by Accelerator Mass Spectrometry

Determining long-lived radionuclide concentrations in radioactive waste has fundamental implications for the long-term management of storage sites. This paper focuses on the measurement of low ¹²⁹I contents in ion exchange resins used for primary fluid purification in Pressurised Water Reactors (PWR). Iodine-129 concentrations were successfully determined using Accelerator Mass Spectrometry (AMS) following a chemical procedure which included (1) acid digestion of resin samples in HNO₃/HClO₄, (2) radioactive decontamination by selective iodine extraction using a new chromatographic resin (CL Resin), and (3) AgI precipitation. Measured ¹²⁹I concentrations ranged from 4 to 12 ng/g, i.e. from 0.03 to 0.08 Bq/g. The calculation of ¹²⁹I/¹³⁷Cs activity ratios used for routine waste management produced values in agreement with the few available data for PWR resin samples.     

The effect of various cations and pH on the adsorption of U(VI) on Amberlite IR-118H resin

The effects of various metal cations and pH on the adsorption of uranium(VI) on strongly acidic cation exchanger Amberlite IR-118H (AIR-118H) were studied. The metal cations suppress U(VI) adsorption differently depending on their ionic radii. Adsorption of U(VI) on AIR-118H peaks at pH 3.4, which was attributed to the occurrence of different forms of U(VI) at different pH values. The adsorption data were then processed using the Frumkin–Fowler–Guggenheim equation, and the standard free energy of adsorption was calculated.     

Normal cranial nerves in the cavernous sinuses: contrast-enhanced three-dimensional constructive interference in the steady state MR imaging

BACKGROUND AND PURPOSE: Three-dimensional (3D) constructive interference in steady state (CISS) MR imaging is useful for demonstrating cranial nerves (CNs) in the cistern. The purpose of this study was to evaluate normal CNs III, IV, V1, V2, and VI in the cavernous sinuses by using contrast-enhanced, three-dimensional (3D), Fourier transformation CISS MR imaging. METHODS: In 76 normal cavernous sinuses from 38 patients, detectability of CNs III-VI in the bilateral cavernous sinuses was evaluated by using contrast-enhanced 3D CISS MR imaging. In 40 cavernous sinuses from 20 patients, contrast-enhanced 3D CISS and contrast-enhanced T1-weighted MR imaging were compared for the detectability of these CNs. RESULTS: Each CN was separately demonstrated, and in 11 patients (29%), all CNs in the cavernous sinuses were identified on contrast-enhanced 3D CISS MR imaging. The images depicted the intracavernous segments of CNs III, IV, V1, V2, and VI in 76 (100%), 46 (61%), 70 (92%), 67 (88%), and 73 (96%) of the 76 sinuses, respectively. In comparison of imaging techniques, contrast-enhanced 3D CISS MR imaging had a detection rate significantly higher than that of enhanced T1-weighting imaging (P < .05) in all CNs except for CN III, which was detected in 100% of cases with both techniques. CONCLUSION: Contrast-enhanced 3D CISS MR imaging provides clear images of each CN in the cavernous segment. This useful method may contribute to the diagnosis of diseases involving the cavernous sinuses, such as Tolosa-Hunt syndrome.     

Preparation of alpha-sources of U(VI) and Th(IV) by the electrodeposition technique in the presence of Ca2+ and some trivalent metals.

A new method for the electrodeposition of uranium and thorium from an aqueous/ethanol media in the presence of Ca(II) and some trivalent metals is described. The deposition is carried out at a constant weak voltage of 30 V and starting current intensity of 3 A. The deposition yields of uranium is investigated as a function of the amounts of various carriers and impurities such as Fe, Al, Bi, La and Ca as well as acetic, nitric and hydrochloric acids. All solutions containing up to 900 ppm of Ca2+ and 100-150 microg of the foreign ions namely: Fe, Bi or La can be used with no chemical separation. Uranium and thorium recoveries between 80 and 96% are obtained and the resolution is typically 25-40 keV. Procedure without chemical purification is proposed for a selective electrodeposition of U(VI) and Th(IV) from one another and from calcium.     

Efficacy of 3,4,3-LIHOPO for reducing neptunium retention in the rat after simulated wound contamination

PURPOSE: The ligand 3,4,3-Li(1,2-HOPO) was tested for Np removal after intramuscular injection of 237Np nitrate in rats. MATERIALS AND METHODS: Two experiments were performed, one with simultaneous injection of neptunium and LIHOPO at dosages ranging from 3 to 200 micromol kg(-1) and the other with delayed administration of LIHOPO 30 micromol kg(-1) from 5 min to 30 min after Np injection. RESULTS: The data obtained after simultaneous injections showed that the ligand dosage effectiveness was not linear and depended on the tissues being considered. For bones, the best results were obtained with 200 micromol kg(-1) LIHOPO, where retention was reduced to 11% of controls. Maximum efficacies for removal in liver and kidney were obtained with 30 micromol kg(-1) LIHOPO, where retention was reduced to 39% and 1.6% of controls, respectively. At higher dosages, LIHOPO seemed to have a reverse effect on these tissues, demonstrated by a significant accumulation of the radionuclide. The delayed administration of LIHOPO dramatically decreased its efficacy. When administered 5 min after Np, LIHOPO was still efficient (60%, 37%, 7% of controls in bone, liver, kidneys, respectively) but not when treatment was delayed to 30 min. CONCLUSIONS: These results demonstrated that LIHOPO was able to complex Np at the wound site but not after translocation to blood.     

Standardization of 237Np

The standardization of ²³⁷Np was investigated. The certified massic activity for ²³⁷Np was obtained by 4παβ liquid scintillation (LS) counting with correction for the ²³³Pa daughter using the CIEMAT/NIST efficiency tracing method using a ³H standard. Confirmatory measurements were also performed by high-resolution HPGe gamma-ray spectrometry, and by 4παβ(LS)-γ(NaI) anticoincidence counting. All results agree within the respective method's uncertainties. It was confirmed that the ²³⁷Np/²³³Pa radioactive equilibrium is disturbed when making dilutions and/or removing aliquots.     

Separation techniques for low-level determination of actinides in soil samples

The separation methods for soil samples applied at PSI are based on extraction chromatography and ion exchange. After sample leaching, the actinides are pre-concentrated via precipitation using oxalic acid. Besides the classical separation methods applying the extraction chromatographic resins U/TEVA™ (for U, Th), TRU™ (Pu, Am), new methods were recently implemented to increase the radiochemical recovery of particularly trivalent Am and Cm. These methods do not require initial reduction of Pu(IV) to Pu(III) but stabilize Pu on the tetravalent oxidation state using a mixture of NaNO₂/H₂O₂ in strong acidic medium. The Pu-fraction is then fixed along with Th onto Dowex AG 1-X2 anion exchanger resin. Th is eluted via complexation with 10 M HCl, Pu via reduction with HI. The fractions of Am+Cm and U are loaded onto DGA™ resin. This resin shows extraordinary high distribution coefficients (k′-values) exceeding 10⁴ (for Am) in strong nitric acid medium. The separation between U and Am is obtained quantitatively by decreasing the HNO₃ concentration from 3 to 0.25 M (stripping of the U-fraction) while Am can be easily eluted thereafter using 0.25 M HCl as complexation compound.