Analytical separation techniques for the determination of chemical warfare agents

Today, the determination of chemical warfare agents (CWAs) is an important area of application in analytical chemistry. Chromatographic, capillary electrophoretic and mass spectrometric techniques are primarily used for the identification and quantification of a broad field of classical CWAs in environmental samples and neutralization masses, obtained after destruction of CWAs. This overview is illustrative for the state of the art and mainly focuses on the literature published since 1996.     

Determination of (236)U and transuranium elements in depleted uranium ammunition by alpha-spectrometry and ICP-MS

It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ((236)U, (239)Pu, (240)Pu, (241)Am, and (237)Np) in the ammunition. In this work the analysis of actinides by alpha-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. (242)Pu and (243)Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri- n-octylamine (TNOA), with a decontamination factor higher than 10(6); after elution plutonium was determined by ICP-MS ((239)Pu and (240)Pu) and alpha-spectrometry ((239+240)Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10(-12) g g(-1) and 2 x 10(-11) g g(-1). The (240)Pu/(239)Pu isotope ratio in one penetrator sample (0.12+/-0.04) was significantly lower than the (240)Pu/(239)Pu ratios found in two soil samples from Kosovo (0.35+/-0.10 and 0.27+/-0.07). (241)Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10(7). The concentration of (241)Am in the penetrator samples was 2.7 x 10(-14) g g(-1) and <9.4 x 10(-15) g g(-1). In addition (237)Np was detected at ultratrace levels. In general, ICP-MS and alpha-spectrometry results were in good agreement.The presence of anthropogenic radionuclides ((236)U, (239)Pu,(240)Pu, (241)Am, and (237)Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of radionuclides are very low, their radiotoxicological effect is negligible.     

Alpha self-irradiation effects in ternary oxides of actinides elements: The zircon-like phases AmVO4 and ANp(VO4)2 (A=Sr, Pb)

We report the experimental studies of irradiation damage from alpha decay in neptunium and americium vanadates versus cumulative dose. The isotopes used were the transuranium α-emitter ²³⁷Np and the α,γ-emitter ²⁴¹Am. Neptunium and americium vanadates self-irradiation was studied by X-ray diffraction method (XRD). The comparison of the powder diffraction patterns reveal that the irradiation has no apparent effect on the neptunium phases while the americium vanadate swells and becomes metamict as a function of cumulative dose.     

Method for the determination of thorium and uranium in urine by ICP-MS

ICP-MS (inductively coupled plasma mass spectrometry) is shown as a very sensitive method for quantitative determination of Th and U concentration and excretion analysis in urine without any sample pretreatment. The current standard method for incorporation monitoring applies alpha-spectrometry, a very tedious and time consuming technique. ICP-MS offers an attractive alternative for monitoring of thorium and uranium body burdens in occupationally exposed subjects and also larger groups of the general population. A limit of determination of 0.5 ng/L in aqueous solutions and 1 ng/L in urine samples for both elements was achieved, with a precision of about ± 10% in the concentration range of appr. 10 ng/L. Due to the lack of a suitable reference material, the accuracy of the method was tested by comparing some of the results with those obtained by -spectrometry, especially for U. There was a sufficient agreement on both results.     

Fast source preparation for alpha-spectrometry of uranium and transuranium isotopes

One of the most important problems related to the high background area is that of environmental contamination. Therefore a number of local plants from Kasar in Köprüba?i as referred to high background area, West Anatolia, were investigated for their uranium contents as well as for other elements by using instrumental neutron activation analysis (INAA). All of the plants except wheat samples contained levels above 0.6 ppm U which is the average background concentration of uranium in the ashed samples of living plant material. Beside the uranium, the concentrations of the other trace elements such as Ce, Ba, Cr, La, Sc, Rb, Fe, Zn, Zr, Eu, Co, Cs, Br, As, Na, K, in the plant ashes were also determined.     

Analytical procedures for the determination of uranium and thorium traces in aluminium

Summary Different combined procedures involving element preconcentration and ICP-OES or polarography are described for the determination of the alpha emitters uranium and thorium in aluminium. The results are compared with those of instrumental neutron activation analysis.After extraction with ethyl acetate, uranium and thorium can be determined by ICP-OES (uranium detection limit, given as 3so, 12 ng/g, standard deviation 0.95 ng/g at 12.5 ng/g; thorium detection limit 8 ng/g, standard deviation 0.9 ng/g at 12.5 ng/g). After a second extraction with tri-n-octyl phosphine oxide, uranium can be determined by polarography (detection limit 10 ng/g, standard deviation 4.4 ng/g at 200 ng/g). Thorium also can be coprecipitated with Fe(OH)₃ and determined with ICP-OES (detection limit 5 ng/g, standard deviation 0.6 ng/g at 10 ng/g).The results obtained by wet chemical analyses lie within the spread of accuracy of the INAA results obtained by several laboratories. In general, the comparative results indicate that super pure aluminium containing less than 1 ng/g uranium and thorium can be produced.The paper has been presented at 12th Colloquium on Materials Analysis, Institute for Analytical Chemistry, Technical University in Vienna, May 13–15, 1985.     

Radiochemical determination of the yields of transuranium nuclides produced from natural uranium irradiated in a reactor

Transuranium nuclides were produced by irradiating a pellet of natural uranium sulfide in the Japan Material Testing Reactor (JMTR). After irradiation, a successive separation of uranium, plutonium, americium and curium was carried out. The fractional concentrations of the nuclides²³⁸Pu,²³⁹Pu,²⁴⁰Pu,²⁴¹Am,²⁴³Am,²⁴²Cm and²⁴⁴Cm were determined by α-ray spectrometry, and those of²⁴¹Pu and^242mAm were estimated from the build-up of α-emitting daughters,²⁴¹Am and²⁴²Cm, respectively. As the yield of²⁴²Pu was too slight to be detected by α-counting, the neutron activation analysis of the plutonium fraction based on the²⁴²Pu(n, γ)²⁴³Pu reaction was carried out by γ-ray spectrometry, and it was shown that a few pg of²⁴²Pu could be determined. A burn-up of²³⁵U was also estimated by neutron activation analysis. The experimental results are compared with the calculated ones.     

IC-ICP-MS applied to the separation and determination of traces of plutonium and uranium in aqueous leachates and acid rinse solutions of UO2 doped with Pu

It is expected that spent nuclear fuel, today mainly UO₂, may become exposed to groundwater after extended storage in a deep geologic repository. After 1000 years, the radioactivity of the fuel will be constituted essentially by α-emissions by long-lived actinides. The α-emissions play a significant role in determining the dissolution behavior of uranium, because the radiolysis of water results in the formation of oxidizing chemical species near the fuel surface. In order to study this effect, UO₂ doped with 0.1 and 10 wt.% of a strong α-emitter (namely ²³⁸Pu) was subject to leaching at room temperature (RT) in deionized water. In order to study the mechanisms of leaching in simulated conditions, very precise and accurate techniques need to be employed. In this paper, the results obtained by inductively coupled plasma mass spectrometry coupled with ion chromatography for the determination of traces of ²³⁸Pu and uranium in aqueous leachates’ solutions are illustrated.     

Comparison of AMS,TIMS, and SIMS techniques for determining uranium isotope ratios in individual particles

The determination of isotope ratios in individual uranium particles is very important for nuclear safeguards. In this work, accelerator mass spectrometry (AMS), thermal ionization mass spectrometry (TIMS), and secondary ion mass spectrometry (SIMS) were applied to isotope ratio analysis of individual uranium particles and compared in terms of background, measurement accuracy, and efficiency. Several individual uranium particles (1–7 μm) from certified reference materials were used as samples. The results show that the average values of blank counting rate of ²³⁵U for AMS, FT-TIMS (FT: fission track), SEM-TIMS (SEM: scanning electron microscope), and SIMS were 7.3, 7.8, 2.7 and 2.2 cps, respectively. The relative error of ²³⁴U/²³⁵U and ²³⁴U/²³⁶U isotope ratios of the particles from U200 for AMS were within 10% and 20%, whereas the results of FT-TIMS and SIMS were within 5% and 10%, respectively. The relative error and external precision of ²³⁴U/²³⁸U and ²³⁵U/²³⁸U of the particles from U850 for the method of AMS, SEM-TIMS, and SIMS were within 10% and 5%, respectively. For ²³⁶U/²³⁸U, the average values of the relative error and external precision measured by AMS were within 5%, which measured by SEM-TIMS and SIMS were all within 10%. AMS has advantages in measuring ²³⁶U/²³⁸U. The measurement time of AMS and SEM-TIMS was shorter than that of FT-TIMS and longer than that of SIMS. It is considered that AMS and SEM-TIMS have a certain development prospect, and it is necessary to research deeply.     

Americium and plutonium separation by extraction chromatography for determination by accelerator mass spectrometry

A simple method was developed to separate Pu and Am using single column extraction chromatography employing N,N,N′,N′-tetra-n-octyldiglycolamide (DGA) resin. Isotope dilution measurements of Am and Pu were performed using accelerator mass spectrometry (AMS) and alpha spectrometry. For maximum adsorption Pu was stabilized in the tetra valent oxidation state in 8 M HNO₃ with 0.05 M NaNO₂ before loading the sample onto the resin. Am(III) was adsorbed also onto the resin from concentrated HNO₃, and desorbed with 0.1 M HCl while keeping the Pu adsorbed. The on-column reduction of Pu(IV) to Pu(III) with 0.02 M TiCl₃ facilitated the complete desorption of Pu. Interferences (e.g. Ca²⁺, Fe³⁺) were washed off from the resin bed with excess HNO₃. Using NdF_3, micro-precipitates of the separated isotopes were prepared for analysis by both AMS and alpha spectrometry. The recovery was 97.7 ± 5.3% and 95.5 ± 4.6% for ²⁴¹Am and ²⁴²Pu respectively in reagents without a matrix. The recoveries of the same isotopes were 99.1 ± 6.0 and 96.8 ± 5.3% respectively in garden soil. The robustness of the method was validated using certified reference materials (IAEA 384 and IAEA 385). The measurements agree with the certified values over a range of about 1–100 Bq kg⁻¹. The single column separation of Pu and Am saves reagents, separation time, and cost.     

Determination of plutonium and americium in environmental samples by inductively coupled plasma sector field mass spectrometry and alpha spectrometry

Application of inductively coupled plasma sector field mass spectrometry (ICP-SFMS) for the determination of americium and plutonium in environmental samples is described in comparison with alpha spectrometry. A sequential sample preparation method was employed using a co-precipitation step for pre-concentration and a separation step applying extraction chromatographic resins. The average recovery of sample preparation calculated from the concentration of the tracer before and after sample treatment was better than 80%. The method development focused on the elimination of possible interferences in mass spectrometric analysis caused by molecular ions (e.g. ²⁰⁰Hg⁴⁰Ar⁺, ²⁰⁴Pb³⁶Ar⁺, ²⁰⁸Pb¹⁶O₂⁺or ²³⁸U¹H⁺) employing matrix separation and desolvation prior to ICP-SFMS analysis. The effect of N₂ gas on signal intensity and oxide ratio was investigated. A two-fold signal improvement was obtained by adding 5 ml min^− 1 N₂ to the sample gas after the desolvation system. For ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu and ²⁴¹Am limit of detection (LOD) of 15, 9.2, 14 and 104 fg g^− 1 was achieved, respectively. Calculation of LOD was based on three times standard deviation of the method blank solution. Absolute detection limit was calculated to be 10-25 fg. For all investigated actinides the precision of the analysis was in the range 0.8-3% relative standard deviation. Results from the analysis of certified reference materials (IAEA-384 and IAEA-385) showed good agreement with recommended values and data available in the literature. The method was applied for analysis of environmental samples originated from Chernobyl and from Mayak region. The possibility of the determination of the origin and date of pollution was demonstrated using isotopic data obtained by ICP-SFMS and alpha spectrometry.     

Performance for PAN-3 chelate fiber for adsorbing and separating trace uranium—determination by ICP-OES

An ICP-OES method is established for polyacrylamidoxime-carboxylic acid chelate fiber (PAN-3) adsorbing and separating trace uranium in waste water. The conditions for quantitative enrichment and desorption uranyl ions are investigated. The stability and the reuse performance of the chelate fiber are discussed. The interference of co-existent ions on uranyl ions as well as the analyses of samples are performed with satisfactory results. The lowest concentration of uranium determined by ICP-OES is 5 g/l, its RSD is 2.6%.     

Synthesis of a cellulose derivative for enhanced sorption and selectivity of uranium from phosphate rocks prior to its fluorometric determination

In this research work, the separation of Uranium from phosphate medium via adsorption prior to its fluorometric determination was carried out onto a newly synthesised adsorbent made via impregnation of urea onto cellulose (UIC). The full characterisation of the synthetic extractant (UIC) was carried out by various instrumental techniques such as elemental analysis, FTIR, TGA, XRD and SEM analysis. Various factors that may affect the quality of adsorbing U (VI) ions using synthesised Urea-impregnated cellulose had been investigated. The maximum adsorption capacity (82 mg/g) for U (VI) has been verified by the Langmuir isotherm model. The thermodynamics and kinetics of the adsorption process indicated that the uranium sorption onto synthesised Urea-impregnated cellulose was an exothermic and pseudo-second-order process. The tolerance limits for the common cations which are actually found with uranium in the phosphate solutions and may show sorption behaviour on the synthesised UIC resin were calculated and gave a high tolerance limit. Contrary to previously reported studies, several ameliorations have resulted including an elevated selectivity and adsorption capacity of uranium from phosphate medium. The optimised method was applied with good accuracy results for determination of uranium in reference and different phosphate rock types bearing uranium.     

Influence of a photochemical reaction on the controlled potential coulometric determination of plutonium in a mixture with uranium

Summary Data are provided in support of a photochemical reaction which takes place simultaneously with the electrochemical reduction of quadrivalent plutonium during the controlled potential coulometric determination of plutonium in a mixture with uranium. The interfering effect of this reaction is overcome by placing the cell in a dark environment.

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Einfluß einer photochemischen Reaktion auf die coulometrische Plutoniumbestimmung neben Uran bei kontrolliertem Potential

Zusammenfassung Es wurde festgestellt, daß bei dieser Bestimmung eine photochemische Reaktion gleichzeitig mit der elektrochemischen Reduktion des vierwertigen Plutoniums abläuft. Experimentelle Beweise werden angeführt. Die Störung kann vermieden werden, wenn die coulometrische Titration im Dunkeln durchgeführt wird.

We wish to thank Mr. R. Batchelor for his interest in this work and Mr. V. Verdingh for his critical comments when drafting this report.     

伊犁盆地ZK0407井褐煤中铀及其他元素的地球化学研究

用数理统计的方法,对伊犁盆地洪海沟地区ZK0407井的中下侏罗统10、11、12号煤层中的铀等59种常量元素、微量元素的地球化学行为进行了探讨。结果表明,元素在灰分的分布和元素在内在水分以及固定碳中的分布呈互为相反数关系,而和元素在挥发分中的分布变化具有同步性。元素和挥发分呈正相关很大程度是因为元素的催化作用和矿物分解产生的一些挥发性组分所造成。ZK0407井在地史上一直位于砂岩层间氧化带的氧化-还原过渡地段,因而也是铀的富矿地段。其煤层为层间氧化带成矿的下翼。U等元素在褐煤中主要以物理吸附的方式存在于其孔隙之中或泥质组分中,有机质对其络合束缚作用,并非U在褐煤中的唯一富集方式。
     

Synthesis of salicylaldehyde-modified mesoporous silica and its application as a new sorbent for separation, preconcentration and determination of uranium by inductively coupled plasma atomic emission spectrometry

A new functionalized mesoporous silica (MCM-41) using salicylaldehyde was utilized for the separation, preconcentration and determination of uranium in natural water by inductively coupled plasma atomic emission spectrometry (ICP-AES).Experimental conditions for effective adsorption of trace levels of U(VI) were optimized. The preconcentration factor was 100 (1.0 mL of elution for a 100 mL sample volume). The analytical curve was linear in the range 2-1000 μg L⁻¹ and the detection limit was 0.5 ng mL⁻¹. The relative standard deviation (R.S.D.) under optimum conditions was 2.5% (n = 10). Common coexisting ions did not interfere with the separation and determination of uranium at pH 5. The sorbent exhibited excellent stability and its sorption capacity under optimum conditions has been found to be 10 mg of uranium per gram of sorbent. The method was applied for the recovery and determination of uranium in different water samples.     

Preparation of soluble ternary heteroazo dye complexes for the spectrophotometric determination of trace uranium(VI)

The complexing ability of typical pyridylazo, quinolylazo and thiazolylazo dyes with uranium(VI) in aqueous ethanol media are investigated in the presence and absence of aromatic carboxylic acid. Uranium(VI) forms solubilized ternary complexes with PAN, PAR, TAM, 5-Br-PADAP, 3,5-diBr-PADAP and QADAP in 48% ethanol solution containing sufficient amounts of sulfosalicylic acid and triethanolamine buffer (pH 7.8). Aromatic carboxylic acids contribute to expel the coordinated water molecules from the uranium (VI) moiety and their chelating effects have been explained by ternary complex formation. An increase in molar absorptivity and no shift in the wavelength of maximum absorbance are observed for all uranium(VI) complexes investigated. The 11 stoichiometry of uranuim(VI) and heteroazo dye in the binary complex does not change through ternary complex formation. The molar absorptivity of the uranium(VI)-3,5-diBr-PADAP-sulfosalicylic acid ternary complex at 595 nm is 8.4×10⁴l mol^–1 cm^–1 and Beer's law is valid up to 2.5gmg ml^–1 of uranium(VI). The interferences due to coexisting metal ions can be effectively masked by addition of CyDTA or Ca-CyDTA.     

Analytical applications of a liquid anion-exchanger for the separation of uranium(IV) in malonate solution

Uranium was quantitatively extracted with 4% Amberlite LA-1 in xylene at pH 2.5-4.0 from 0.001 M malonic acid. It was stripped from the organic phase with 0.01 M sodium hydroxide and determined spectrophotometrically at 530 nm as its complex with 4-(2-pyridylazo) resorcinol. Of various liquid anion-exchangers tested, Amberlite LA-1 was found to be best. Uranium was separated from alkali and alkaline earth metal ions, thallium(I), iron(II), silver, arsenic(III) and tin(IV) by selective extraction, and from zinc, cadmium, nickel, copper(II), cobalt(II), chromium(III), aluminium, iron(III), lead, bismuth, antimony(III) and yttrium by selective stripping. The separation from scandium, zirconium, thorium and vanadium(V) was done by exploiting differences in the stability of chloro-complexes.