Comparison of ICP-MS and SIMS techniques for determining uranium isotope ratios in individual particles

The determination of uranium isotope ratios in individual particles is of great importance for nuclear safeguards. In the present study, an analytical technique by inductively coupled plasma mass spectrometry (ICP-MS) with a desolvation sample introduction system was applied to isotope ratio analysis of individual uranium particles. In ICP-MS analysis of individual uranium particles with diameters ranging from 0.6 to 4.2 μm in a standard reference material (NBL CRM U050), the use of the desolvation system for sample introduction improved the precision of ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope ratios. The performance of ICP-MS with desolvation was compared with that of a conventionally used method, i.e., secondary ion mass spectrometry (SIMS). The analysis of test swipe samples taken at nuclear facilities implied that the performance of ICP-MS with desolvation was superior to that of SIMS in a viewpoint of accuracy, because the problems of agglomeration of uranium particles and molecular ion interferences by other elements could be avoided. These results indicated that ICP-MS with desolvation has an enough ability to become an effective tool for nuclear safeguards.     

Introducing wet aerosols into the static high sensitivity ICP (SHIP)

A demountable design of the static high sensitivity ICP (SHIP) for optical emission spectrometry is presented, and its use as an excitation source with the introduction of wet aerosols was investigated. Aerosols were produced by standard pneumatic sample introduction systems, namely a cross flow nebulizer, Meinhard nebulizer and PFA low flow nebulizer, which have been applied in conjunction with a double pass and a cyclonic spray chamber. The analytical capabilities of these sample introduction systems in combination with the SHIP system were evaluated with respect to the achieved sensitivity. It was found that a nebulizer tailored for low argon flow rates (0.3–0.5 L min⁻¹) is best suited for the low flow plasma (SHIP). An optimization of all gas flow rates of the SHIP system with the PFA low flow nebulizer was carried out in a two-dimensional way with the signal to background ratio (SBR) and the robustness as optimization target parameters. Optimum conditions for a torch model with 1-mm injector tube were 0.25 and 0.36 L min⁻¹ for the plasma gas and the nebulizer gas, respectively. A torch model with a 2-mm injector tube was optimized to 0.4 L min⁻¹ for the plasma gas and 0.44 L min⁻¹ for the nebulizer gas. In both cases the SHIP system saves approximately 95% of the argon consumed by conventional inductively coupled plasma systems. The limits of detection were found to be in the low microgram per litre range and below for many elements, which was quite comparable to those of the conventional setup. Furthermore, the short-term stability and the wash out behaviour of the SHIP were investigated. Direct comparison with the conventional setup indicated that no remarkable memory effects were caused by the closed design of the torch. The analysis of a NIST SRM 1643e (Trace Elements in Water) with the SHIP yielded recoveries of 97–103% for 13 elements, measured simultaneously. Photo of the SHIP-III during operation     

Dual nebulizer sample introduction system for simultaneous determination of volatile elemental hydrides and other elements

A dual sample introduction system was explored for volatile hydride generation in inductively coupled plasma–optical emission spectrometry (ICP–OES) performed in the radially viewed mode. The system consists of two pneumatic nebulizers connected to the conventional spray chamber of the instrument via a simple adaptor. This configuration permits hydride generation but still allows other elements to be determined by pneumatic nebulization. This work was focused on the optimization of the plasma operating conditions for the determination of As, Hg, Sb and Se and other elements. The excitation conditions of the ICP–OES instrument operated with the dual sample introduction system were also explored. Results showed that the analytical performance of the dual system for the determination of As, Hg, Sb and Se was superior to those of conventional nebulization systems. The dual system also enabled the determination of elements that do not form volatile hydrides, but with less sensitivity than conventional nebulization systems. An evaluation of the plasma robustness showed that the gases generated in the hydride reactions did not significantly affect the plasma discharge. Similar to conventional hydride generation techniques, the analysis was susceptible to nonspectroscopic interferences produced by transition metals. Finally, the applicability of the dual nebulization system to practical ICP–OES studies was demonstrated by determining the trace elements in an oyster tissue standard reference material.      

Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry

Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the ²⁴¹Pu/²³⁹Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles.     

Simultaneous determination of hydride (Se) and non-hydride-forming (Ca,Mg, K,P, S and Zn) elements in various beverages (beer,coffee, and milk), with minimum sample preparation,by ICP–AES and use of a dual-mode sample-introduction system

A method has been developed enabling direct analysis (i.e. after dilution only) of beer, instant coffee, milk, and milk powder by ICP–AES. Analysis of the beverages after dilution with a low concentration of HNO₃ was used for accurate determination of essential minor and trace elements (Ca, Mg, K, P, S, and Zn). Selenium, introduced as the hydride, was determined simultaneously with the other non-hydride-forming elements using the commercial multi-mode sample-introduction system (MSIS). To obtain accurate results, however, some simple pre-treatment was needed. Analysis was also performed after microwave-assisted decomposition of the samples. Three different modes of sample-preparation, i.e. dilution only, partial decomposition (aqua regia treatment), and complete decomposition were compared. The results obtained by use of the three different sample-preparation methods were in very good agreement. Results from analysis of certified reference material (SRM 1459 non-fat milk powder) also verified the accuracy of the methods. The limit of detection obtained for Se using dual-mode sample introduction was 0.5 ng mL^–1, which corresponds to approximately 2 ng g^–1 in beer and approximately 4 ng g^–1 in coffee and milk when using the recommended procedure.     

Effect of droplet size on the phosphine depression of calcium atomic emission signals in flame spectrometry

The effect of the droplet size on the magnitude of the phosphine depression of calcium signals is discussed. The droplet size governs the time required for droplet desolvation in the flame. It is during the desolvation process that the combustion products of phosphine, PO_x, diffuse into the droplet and form a refractory compound with the analyte. The longer the desolvating droplet resides in the PO_x-contaminated flame, the more severe the depression. A uniform droplet generator, a pneumatic nebulizer spray chamber system, and a glass-frit nebulizer spray chamber system were the sample introduction systems studied. Droplet sizes of (55 μm, 0.5–10 μm (2 μm mean), and <0.1–2 μm (0.1 μm mean) were produced by these systems, respectively, and depressions of the calcium signals of 57%, 55%, and 4% were noted. These results suggest that the phosphine depression on calcium signals may be alleviated by using a glass-frit nebulizer (or modifying a commercial nebulizer) to remove droplets greater than 2 μm in diameter.     

Interfacing a microchip-based capillary electrophoresis system with a microwave induced plasma spectrometry for copper speciation

A microchip-based capillary electrophoresis (μCE) system was interfaced with a microwave induced plasma optical emission spectrometry (MIP-OES) to provide copper species separation capabilities. This system uses an extremely low flow demountable direct injection high efficiency nebulizer (D-DIHEN) sited directly at the liquid exit of the chip. A supplementary flow of buffer solution at the channel exit was used to improve nebulization efficiency. A small evaporation chamber has been incorporated into the interface in order to prevent the losses associated with traditional spray chambers, allowing the entire aerosol sample to enter the plasma. Syringe pumps were used to manipulate the flow rate and flow direction of the sample, buffer, and supplementary buffer solution. Sample volumes of 25 nL can be analyzed. With application of an electric field up to 500 V cm⁻¹, species such as Cu(II) and Cu(EDTA)²⁻ were separated in acidic solution within 90 s using a 26 mm long separation channel etched in a glass base. Resolution of the Cu(II) and Cu(EDTA)²⁻ peaks was 1.1 using the chip-based μCE-MIP-OES system.      

Determination of compound-specific Hg isotope ratios from transient signals using gas chromatography coupled to multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS)

MeHg and inorganic Hg compounds were measured in aqueous media for isotope ratio analysis using aqueous phase derivatization, followed by purge-and-trap preconcentration. Compound-specific isotope ratio measurements were performed by gas chromatography interfaced to MC-ICP/MS. Several methods of calculating isotope ratios were evaluated for their precision and accuracy and compared with conventional continuous flow cold vapor measurements. An apparent fractionation of Hg isotopes was observed during the GC elution process for all isotope pairs, which necessitated integration of signals prior to the isotope ratio calculation. A newly developed average peak ratio method yielded the most accurate isotope ratio in relation to values obtained by a continuous flow technique and the best reproducibility. Compound-specific isotope ratios obtained after GC separation were statistically not different from ratios measured by continuous flow cold vapor measurements. Typical external uncertainties were 0.16‰ RSD (n = 8) for the ²⁰²Hg^/198Hg ratio of MeHg and 0.18‰ RSD for the same ratio in inorganic Hg using the optimized operating conditions. Using a newly developed reference standard addition method, the isotopic composition of inorganic Hg and MeHg synthesized from this inorganic Hg was measured in the same run, obtaining a value of δ ²⁰²Hg = −1.49 ± 0.47 (2SD; n = 10). For optimum performance a minimum mass of 2 ng per Hg species should be introduced onto the column.     

Internal correction of spectral interferences and mass bias for selenium metabolism studies using enriched stable isotopes in combination with multiple linear regression

The analytical methodology for the in vivo study of selenium metabolism using two enriched selenium isotopes has been modified, allowing for the internal correction of spectral interferences and mass bias both for total selenium and speciation analysis. The method is based on the combination of an already described dual-isotope procedure with a new data treatment strategy based on multiple linear regression. A metabolic enriched isotope (⁷⁷Se) is given orally to the test subject and a second isotope (⁷⁴Se) is employed for quantification. In our approach, all possible polyatomic interferences occurring in the measurement of the isotope composition of selenium by collision cell quadrupole ICP-MS are taken into account and their relative contribution calculated by multiple linear regression after minimisation of the residuals. As a result, all spectral interferences and mass bias are corrected internally allowing the fast and independent quantification of natural abundance selenium (^natSe) and enriched ⁷⁷Se. In this sense, the calculation of the tracer/tracee ratio in each sample is straightforward. The method has been applied to study the time-related tissue incorporation of ⁷⁷Se in male Wistar rats while maintaining the ^natSe steady-state conditions. Additionally, metabolically relevant information such as selenoprotein synthesis and selenium elimination in urine could be studied using the proposed methodology. In this case, serum proteins were separated by affinity chromatography while reverse phase was employed for urine metabolites. In both cases, ⁷⁴Se was used as a post-column isotope dilution spike. The application of multiple linear regression to the whole chromatogram allowed us to calculate the contribution of bromine hydride, selenium hydride, argon polyatomics and mass bias on the observed selenium isotope patterns. By minimising the square sum of residuals for the whole chromatogram, internal correction of spectral interferences and mass bias could be accomplished. As a result, the tracer/tracee ratio could be calculated for each selenium-containing species and a time relationship for synthesis and degradation established. Both selenite and selenized yeast labelled with ⁷⁷Se were employed for comparative purposes.     

Internal correction of hafnium oxide spectral interferences and mass bias in the determination of platinum in environmental samples using isotope dilution analysis

A method has been developed for the accurate determination of platinum by isotope dilution analysis, using enriched ¹⁹⁴Pt, in environmental samples containing comparatively high levels of hafnium without any chemical separation. The method is based on the computation of the contribution of hafnium oxide as an independent factor in the observed isotope pattern of platinum in the spiked sample. Under these conditions, the ratio of molar fractions between natural abundance and isotopically enriched platinum was independent of the amount of hafnium present in the sample. Additionally, mass bias was corrected by an internal procedure in which the regression variance was minimised. This was possible as the mass bias factor for hafnium oxide was very close to that of platinum. The final procedure required the measurement of three platinum isotope ratios (192/194, 195/194 and 196/194) to calculate the concentration of platinum in the sample. The methodology has been validated using the reference material “BCR-723 road dust” and has been applied to different environmental matrices (road dust, air particles, bulk wet deposition and epiphytic lichens) collected in the Aspe Valley (Pyrenees Mountains). A full uncertainty budget, using Kragten’s spreadsheet method, showed that the total uncertainty was limited only by the uncertainty in the measured isotope ratios and not by the uncertainties of the isotopic composition of platinum and hafnium. Figure Simultaneous correction of hafnium oxide spectral interferences and mass bias in the determination of platinum in environmental samples using isotope dilution analysis Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Computerized simulation of aerosol-droplet desolvation in an inductively coupled plasma

A mathematical model for the desolvation of solvent droplets has been used in conjunction with an existing code for simulation of ICP fundamental parameters. The combination has been used for the calculation of droplet histories and desolvation behavior along the central channel of an ICP. Calculations have been performed for droplets of various sizes and under a variety of ICP operating conditions. As central-channel gas flow rate increases, the point of complete desolvation of the droplet shifts upward in the plasma, away from the load coil. This relationship is fairly linear. As forward power increases, the point of complete desolvation moves down in the discharge, closer to the load coil. This is approximately an inverse relationship. Finally, simulation of behavior for a log-normal size distribution of a large number of droplets (10⁸) shows that the number of surviving droplets falls sigmoidally with height above the load coil. For most nebulizer/spray chamber systems, the desolvation process is complete at a well-defined height in the plasma.     

Development of an accurate,sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine,sulfur, and heavy metals) in coal samples

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for ³⁵Cl⁺ to more than 6 × 10⁵ cps for ²³⁸U⁺ for 1 μg of trace element per gram of coal sample. Detection limits vary from 450 ng g⁻¹ for chlorine and 18 ng g⁻¹ for sulfur to 9.5 pg g⁻¹ for mercury and 0.3 pg g⁻¹ for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis. Figure LA-ICP-IDMS allows direct multi-element determination in powdered coal samples     

Total selenium and selenomethionine in pharmaceutical yeast tablets: assessment of the state of the art of measurement capabilities through international intercomparison CCQM-P86

Results of an international intercomparison study (CCQM-P86) to assess the analytical capabilities of national metrology institutes (NMIs) and selected expert laboratories worldwide to accurately quantitate the mass fraction of selenomethionine (SeMet) and total Se in pharmaceutical tablets of selenised-yeast supplements (produced by Pharma Nord, Denmark) are presented. The study, jointly coordinated by LGC Ltd., UK, and the Institute for National Measurement Standards, National Research Council of Canada (NRCC), was conducted under the auspices of the Comité Consultatif pour la Quantité de Matière (CCQM) Inorganic Analysis Working Group and involved 15 laboratories (from 12 countries), of which ten were NMIs. Apart from a protocol for determination of moisture content and the provision of the certified reference material (CRM) SELM-1 to be used as the quality control sample, no sample preparation/extraction method was prescribed. A variety of approaches was thus used, including single-step and multiple-step enzymatic hydrolysis, enzymatic probe sonication and hydrolysis with methanesulfonic acid for SeMet, as well as microwave-assisted acid digestion and enzymatic probe sonication for total Se. For total Se, detection techniques included inductively coupled plasma (ICP) mass spectrometry (MS) with external calibration, standard additions or isotope dilution MS (IDMS), inductively coupled plasma optical emission spectrometry , flame atomic absorption spectrometry and instrumental neutron activation analysis. For determination of SeMet in the tablets, five NMIs and three academic/institute laboratories (of a total of five) relied upon measurements using IDMS. For species-specific IDMS measurements, an isotopically enriched standard of SeMet (⁷⁶Se-enriched SeMet) was made available. A novel aspect of this study relies on the approach used to distinguish any errors which arise during analysis of a SeMet calibration solution from those which occur during analysis of the matrix. To help those participants undertaking SeMet analysis to do this, a blind sample in the form of a standard solution of natural abundance SeMet in 0.1 M HCl (with an expected value of 956 mg kg⁻¹ SeMet) was provided. Both high-performance liquid chromatography (HPLC)–ICP-MS or gas chromatography (GC)–ICP-MS and GC-MS techniques were used for quantitation of SeMet. Several advances in analytical methods for determination of SeMet were identified, including the combined use of double IDMS with HPLC-ICP-MS following extraction with methanesulfonic acid and simplified two-step enzymatic hydrolysis with protease/lipase/driselase followed by HPLC-ICP-IDMS, both using a species-specific IDMS approach. Overall, satisfactory agreement amongst participants was achieved; results averaged 337.6 mg kg⁻¹ (n = 13, with a standard deviation of 9.7 mg kg⁻¹) and 561.5 mg kg⁻¹(n = 11, with a standard deviation of 44.3 mg kg⁻¹) with median values of 337.6 and 575.0 mg kg⁻¹ for total Se and SeMet, respectively. Recovery of SeMet from SELM-1 averaged 95.0% (n = 9). The ability of NMIs and expert laboratories worldwide to deliver accurate results for total Se and SeMet in such materials (selensied-yeast tablets containing approximately 300 mg kg⁻¹ Se) with 10% expanded uncertainty was demonstrated. The problems addressed in achieving accurate quantitation of SeMet in this product are representative of those encountered with a wide range of organometallic species in a number of common matrices. Figure Looking into the quantitative speciation of selenium in pharmaceutical supplements Photo courtesy of LGC.     

The influence of the sample introduction system on signals of different tin compounds in inductively coupled plasma-based techniques

The influence of the sample introduction system on the signals obtained with different tin compounds in inductively coupled plasma (ICP) based techniques, i.e., ICP atomic emission spectrometry (ICP–AES) and ICP mass spectrometry (ICP–MS) has been studied. Signals for test solutions prepared from four different tin compounds (i.e., tin tetrachloride, monobutyltin, dibutyltin and di-tert-butyltin) in different solvents (methanol 0.8% (w/w), i-propanol 0.8% (w/w) and various acid matrices) have been measured by ICP–AES and ICP–MS. The results demonstrate a noticeable influence of the volatility of the tin compounds on their signals measured with both techniques. Thus, in agreement with the compound volatility, the highest signals are obtained for tin tetrachloride followed by di-tert-butyltin/monobutyltin and dibutyltin.The sample introduction system exerts an important effect on the amount of solution loading the plasma and, hence, on the relative signals afforded by the tin compounds in ICP–based techniques. Thus, when working with a pneumatic concentric nebulizer, the use of spray chambers affording high solvent transport efficiency to the plasma (such as cyclonic and single pass) or high spray chamber temperatures is recommended to minimize the influence of the tin chemical compound. Nevertheless, even when using the conventional pneumatic nebulizer coupled to the best spray chamber design (i.e., a single pass spray chamber), signals obtained for di-tert-butyltin/monobutyltin and dibutyltin are still around 10% and 30% lower than the corresponding signal for tin tetrachloride, respectively. When operating with a pneumatic microconcentric nebulizer coupled to a 50 °C-thermostated cinnabar spray chamber, all studied organotin compounds provided similar emission signals although about 60% lower than those obtained for tin tetrachloride. The use of an ultrasonic nebulizer coupled to a desolvation device provides the largest differences in the emission signals, among all tested systems.     

Influence of heated spray chamber desolvation on the detectability in inductively coupled plasma atomic emission spectrometry

 A comparison study has been made of the performance of a heated spray chamber desolvation system for sample introduction into inductively coupled plasma. The heated spray chamber system Mistral replaces the normal spray chamber of an ICP-spectrometer and improves the efficiency of both aerosol generation and transport to the plasma [1]. 27 elements in 6 sample solutions with different mineralization were measured with and without the heated spray chamber system. The higher the mineralization of the sample solution, the less was the increase of the intensity of the spectral lines of the elements determined. An increase of the intensity by the same factor for most of the elements was observed in different sample solutions like drinking water (factor 6), fresh water (factor 5), sea water (factor 1.5) and acid solutions resulting from the digestions of soil (factor 3–4) and rock (factor 2) samples. A few elements in drinking and fresh water were only detectable by using Mistral. A clear improvement of the detection limits was found, but compared to the increase of the intensity not for all elements by the same factor. The detection limits for water samples are in the lower μg/L- and the higher ng/L-level by using Mistral. So the Mistral is an alternative to the ultrasonic nebulizer. Received: 28 November 1995/Revised: 15 February 1996/Accepted: 21 February 1996     

Determination of ultra-trace amounts of inorganic selenium species in natural water by ion chromatography-inductively coupled plasma-mass spectrometry coupled with nano-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> solid phase extraction

This work presents a nano-Al₂O₃ solid phase extraction technique for the determination of ultra-trace amounts of inorganic selenium species in aqueous systems using ion chromatography inductively coupled plasma-mass spectrometry (IC-ICP-MS). In this experiment, the inorganic selenium species were successfully extracted on a nano-Al₂O₃ solid phase column and then quantitative eluted with a 100 mmol L⁻¹ NaOH solution. Extraction conditions such as solvent identity, solvent concentration, solvent volume, solvent pH and salt addition were optimized. Under the optimum extraction conditions (elute solvent: 100 mmol L⁻¹ NaOH, solvent volume: 4 mL, pH: 7.0), low detection limits (Se (IV): 6 ng L⁻¹, Se (VI): 11 ng L⁻¹; RSD<5.0%) and good linear range (0.5–100 ng mL⁻¹, R² > 0.999) were obtained for all of the analytes. Good spiked recoveries over the range of 80–98% were obtained by applying the proposed method on real environmental water samples. These results indicated that this method is very sensitive and reliable when monitoring trace levels of inorganic selenium species in aqueous samples.      

Accurate purification age determination of individual uranium–plutonium mixed particles

Age of individual uranium–plutonium (U/Pu) mixed particles with various U/Pu atomic ratios (1–70) were determined by inductively coupled plasma mass spectrometry. Micron-sized particles were prepared from U and Pu certified reference materials. The Pu reference was stored for 4–6 years since the last purification (July 14, 2008). The Pu purification age was obtained from the ²⁴¹Am/²⁴¹Pu ratio which was calculated from the product of three measured ratios of Pu and Am isotopes in the eluted fractions. These ratios were measured by a high-resolution inductively coupled plasma mass spectrometer equipped with a desolvation system. Femto-gram to pico-gram quantities of Am, U, and Pu in a sample solution were sequentially separated on a small anion-exchange column. The ²⁴¹Am/²⁴¹Pu ratio was accurately determined by spiking pure ²⁴³Am into the sample solution. The average determined age for the particles for the five independent U/Pu ratios was in good agreement with the expected age with high accuracy (difference age 0.27 years) and high precision (standard deviation 0.44 years). The described analytical technique can serve as an effective tool for nuclear safeguards and environmental radiochemistry.

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Figure Young (4?6 y) Pu purification age of individual U/Pu mixed micron-sized reference particles for the five independent U/Pu ratios (1?70) were determined with 0.27±0.44 y difference from the expected age. Sub pico-gram quantities of Am, U and Pu were sequentially separated a small column, and their isotope ratios were accurately measured using an ICP-MS by applying the ²⁴³Am spiking technique to the analysis and correcting the impurity and the contaminations.

     

A Spectroscopic Overview of Intramolecular Hydrogen Bonds of NH…O,S,N Type

Intramolecular NH…O,S,N interactions in non-tautomeric systems are reviewed in a broad range of compounds covering a variety of NH donors and hydrogen bond acceptors. ¹H chemical shifts of NH donors are good tools to study intramolecular hydrogen bonding. However in some cases they have to be corrected for ring current effects. Deuterium isotope effects on ¹³C and ¹⁵N chemical shifts and primary isotope effects are usually used to judge the strength of hydrogen bonds. Primary isotope effects are investigated in a new range of magnitudes. Isotope ratios of NH stretching frequencies, νNH/ND, are revisited. Hydrogen bond energies are reviewed and two-bond deuterium isotope effects on ¹³C chemical shifts are investigated as a possible means of estimating hydrogen bond energies.     

Determination of norfloxacin in human urine by capillary electrophoresis with electrochemiluminescence detection

A fast and sensitive approach that can be used to detect norfloxacin in human urine using capillary electrophoresis with end-column electrochemiluminescence (ECL) detection of is described. The separation column was a 75-μm i.d. capillary. The running buffer was 15 mmol L⁻¹ sodium phosphate (pH 8.2). The solution in the detection cell was 50 mmol L⁻¹ sodium phosphate (pH 8.0) and 5 mmol L⁻¹ The ECL intensity varied linearly with norfloxacin concentration from 0.05 to 10 μmol L⁻¹. The detection limit (S/N=3) was 0.0048 μmol L⁻¹, and the relative standard deviations of the ECL intensity and the migration time for eleven consecutive injections of 1.0 μmol L⁻¹ norfloxacin (n=11) were 2.6% and 0.8%, respectively. The method was successfully applied to the determination of norfloxacin spiked in human urine without sample pretreatment. The recoveries were 92.7–97.9%.      

Effect of nebulizer/spray chamber interfaces on simultaneous,axial view inductively coupled plasma optical emission spectrometry for the direct determination of As and Se species separated by ion exchange high-performance liquid chromatography

Different nebulizer/expansion chamber combinations were evaluated to assess their performance for sample introduction in the direct coupling with an axial view inductively coupled plasma multielement spectrometer for on-line determination of As and Se species previously separated by ion exchange–high performance liquid chromatography. The column effluents were injected into the plasma without prior derivatization. The instrument operation software was adapted for data acquisition and processing to allow multi-wavelength recording of the transient chromatographic peaks. After optimization of the chromatographic operating conditions, separation of mixtures of inorganic As and Se species, and of inorganic and two organic As species (monomethylarsonic and dimethylarsinic acids), was achieved with excellent resolution. Species discrimination from mixtures of As and Se oxyanions was further improved by the simultaneous element detection at specific analytical wavelengths. Three nebulizers and three spray chambers, employed in seven combinations, were tested as interfaces. Concentric nebulizers associated to a glass cyclonic chamber appear most suitable regarding sensitivity and signal to noise ratio. Measured element detection limits (3 σ) were around 10 ng ml^− 1 for all the species considered, making the method a viable alternative to similar procedures that employ volatile hydride generation previous to sample injection into the plasma. Analytical recoveries both for inorganic and organic species ranged between 92 and 107%. The method was demonstrated to be apt for the analysis of surface waters potentially subjected to natural contamination with arsenic.