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1.
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.  相似文献   

2.
A method is described for labeling and measuring the incorporation of dietary copper into hair using the enriched (99.61 atomic-%) 65Cu isotope. Natural isotope abundant copper exists as 65Cu (30.86 atomic-%) and 63Cu (69.17 atomic-%), but enriched (99.61 atomic-%) 65Cu isotope may be obtained commercially and administered to change deliberately the natural isotope abundance of copper to “label” the copper source. Natural isotope abundant copper and the enriched (99.61 atomic-%) 65Cu isotope were mixed into rat feed and administered daily by gavage. The isotope concentration was determined by neutron activation analysis (NAA). The copper concentration was determined by direct-current argon plasma (DCP) spectrometry.The measured copper isotope ratios (65Cu/Cutot)_for the natural isotope abundant copper in National Bureau of Standards Standard Reference Materials (NBS SRM) 1571 Orchard Leaves and 1577a Bovine Liver were 0.3201 ± 0.0039 and 0.3187 ± 0.0089, respectively. Measured copper isotope ratios in rat hair were 0.3100 ± 0.0606, 0.4580 ± 0.2495 and 0.2712 ± 0.0645 from rats given a standard feed that contained natural isotope abundant copper, a daily supplement of natural isotope abundant copper sulfate mixed into the standard feed and a daily supplement of copper sulfate administered by gavage, respectively. The copper isotope ratio increased to 0.5251 ± 0.2860 and 0.7235 ± 0.0704 in hair from rats given enriched 65Cu in their feed and by gavage, respectively. The statistically significant increase in the 65Cu isotope when administered by gavage demonstrates strates successful labeling of dietary copper in the hair.  相似文献   

3.
Undigested honey samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using direct injection nebulization (DIN). Samples were diluted 25-fold using dilute HNO3 to which Triton X-100 was added. Isotope dilution (ID) was used to quantify Ba, Cu, Pb and Zn in these natural matrix samples. DIN parameters were optimized to obtain a stable transient signal enough to determine multiple isotope ratios. The Ba, Cu and Zn isotope ratios were measured in a single sample injection of 50 μl diluted honey and the Pb isotopes in a separate injection. The analysis was characterized by precisions given by R.S.D. values from 0.20 to 1.24% for Ba, 0.49–1.23% for Cu, 0.61–2.28% for Pb and 0.50–1.51% for Zn. The results were in agreement, at the 95% confidence level, with those obtained by analyzing digested samples using external calibration. Using this direct method, 30 real honey samples per hour could be analyzed.  相似文献   

4.
The kinetics of zinc absorption, metabolism and excretion is extensively studied by nutritionists. Stable isotopes of zinc can be used to identify body zinc compartments that have different turnover kinetics. Since the compartments might belong to physiological subsections of different organs, there is a need for microsampling analysis to determine isotope ratios of the trace element zinc in tissue samples. Here, we study the feasibility to use laser ablation coupled to quadrupole ICP-MS for the determination of zinc tracers given to rats at different time points with the aim to generate isotope ratio bioimages of heart tissue. A double tracer (70Zn and 67Zn) experiment with rats was designed to label the exchangeable zinc pool as well as the stable zinc pool. The isotope ratios determined by laser ablation ICP-MS were evaluated by additional measurements of tissue digests. Accumulated tracers which made up more than 0.1% of total zinc could be identified in the tissues of the treated rats. It was established that at least 50 measurements from the microsampling were necessary to distinguish between controls and a tracer treated rat resulting in reduced resolution of the bioimage. With the parameters used, features in the tissue thin sections of at least 250 μm2 in size are necessary to detect the incorporation of a tracer. When different time points have to be measured, higher precisions are required and therefore a larger area needs to be ablated (1 mm2). Using the bioimages and pool measurements from one physiological feature, it was possible to show that the aorta cell walls incorporate the zinc tracer at the different time points.  相似文献   

5.
Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP–MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP–MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP–MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample.  相似文献   

6.
Esaka F  Magara M  Suzuki D  Miyamoto Y  Lee CG  Kimura T 《Talanta》2010,83(2):569-573
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.  相似文献   

7.
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.  相似文献   

8.
Summary Isotope dilution mass spectrometry (IDMS) as a definitive method is a sensitive analytical technique for accurate trace analysis down to the sub-ppb level. The application of IDMS requires precise and accurate isotope ratio measurements. It has been demonstrated that these measurements can be carried out with a small, cost-efficient and easy-to-use quadrupole mass spectrometer equipped with both a Faraday detector and a secondary electron multiplier (SEM). Here we describe a new detector system for this instrument which allows pulse counting measurements of both positive and negative ions. The performance of the new detector system is shown for I, Sr and Nd isotope ratio measurements. A synthetic mixture of127I and129I was measured using negative thermal ionisation. The127I/129I isotope ratio was determined with a relative external precision of 0.6% using I loadings of 0.08 and 0.8 nmol. For Sr and Nd isotope ratios a relative external precision of 0.1%–0.2% and an accuracy of 0.06% were obtained for loadings of 0.01 to 0.05 nmol.
Bestimmung von Iod-, Strontium- und Neodym-Isotopenverhältnissen bei Verwendung eines Thermionen-Quadrupol-Massenspektrometers mit Einzelionenzähleinrichtung
  相似文献   

9.
Negative health effects of uranium taken into the human body are related to both the chemical toxicity of the metal and its radioactivity. A simple and reliable isotope dilution ICP-MS uranium bioassay technique was developed in this study. Use of this technique at Los Alamos National Laboratory has not been previously described. Dilute urine was introduced to a Perkin Elmer DRC II quadrupole ICP-MS via a PFA high solids nebulizer and a PFA cyclonic spray chamber cooled to 2 °C. Urine samples acidified, digested, and diluted 5× generate a solution that is roughly 10% HNO3 that can be analyzed by ICP-MS to measure uranium concentrations >54 pg/mL and uranium isotopic ratios with high enough precision and accuracy to determine if the uranium in a urine sample is natural. A three-stage rinsing routine is run between each sample to minimize urine salt deposition and uranium memory effects. Regular use of this rinsing routine minimizes instrumental drift and has produced a running 238U background of <7 cps.  相似文献   

10.
Fujii T  Suzuki D  Watanabe K  Yamana H 《Talanta》2006,69(1):32-36
The total evaporation technique of thermal ionization mass spectrometry was applied to the isotopic analysis of chromium. High measurement reproducibility of the chromium isotope ratios was verified (2 S.E. < 0.05% (53Cr/52Cr)), while a clear mass fractionation effect was observed by using conventional measurement technique. The chromium isotope ratios analyzed by the total evaporation method were not affected by the sample amount on the rhenium filament (50-500 ng Cr). The isotopic analysis under the coexistence of zinc was also performed, and its effect to the chromium isotope ratios was confirmed.  相似文献   

11.
A quantitative methodology has been developed to differentiate between endogenous and supplemented selenium in lactating rats using two enriched selenium isotopes. Lactating rats were fed for 2 weeks with formula milk containing one enriched Se isotope, 77Se, as the metabolic tracer. The isotopic composition of selenium in serum and urine samples was then measured by collision cell ICP-MS after the addition of a solution containing another enriched isotope, 74Se, as quantitation tracer, before analysis. Isotope pattern deconvolution allowed the transformation of measured Se isotopic abundances into concentrations of natural abundance (endogenous) selenium and enriched 77Se (supplemented) present in the samples. The proposed methodology was validated using serum and urine reference materials spiked with both 77Se and 74Se. The obtained results are discussed in terms of selenium exchange and half-life in lactating rats (11–12 days) and selenium levels in serum in comparison with non-supplemented rats and control rats after maternal feeding.  相似文献   

12.
The capability of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of uranium isotope ratios in individual particles was determined. For this purpose, we developed an experimental procedure including single particle transfer with a manipulator, chemical dissolution and isotope ratio analysis, and applied to the analysis of individual uranium particles in certified reference materials (NBL CRM U050 and U350). As the result, the 235U/238U isotope ratio for the particle with the diameter between 0.5 and 3.9 μm was successfully determined with the deviation from the certified ratio within 1.8%. The relative standard deviation (R.S.D.) of the 235U/238U isotope ratio was within 4.2%. Although the analysis of 234U/238U and 236U/238U isotope ratios gave the results with inferior precision, the R.S.D. within 20% was possible for the measurement of the particle with the diameter more than 2.1 μm. The developed procedure was successfully applied to the analysis of a simulated environmental sample prepared from a mixture of indoor dust (NIST SRM 2583) and uranium particles (NBL CRM U050, U350 and U950a). From the results, the proposed procedure was found to be an alternative analytical tool for nuclear safeguards.  相似文献   

13.
Isotope dilution analysis method coupled with flow injection and inductively coupled plasma mass spectrometry (ID-FI-ICP-MS), enabled trace lead concentration in seawater to be determined and the high salt concentration in the matrix, such as Na+, Ca2+ and Mg2+, to be removed on-line. The operational parameters of the FI system including pH for the chelating reaction, concentration of 8-hydroxyquinoline-5-sulfonic acid (8-HQS), sample loading time and injection speed, washing time and speed, eluting acid concentration and eluting speed, and instrumental parameters for ICP-MS were optimized and selected. Accurate results could be achieved because the isotope ratios required can be precisely measured in the range of the eluting peak by means of ID-FI-ICP-MS. The 3σ detection limit was 0.204 ng ml−1. The trace lead concentration of seawater in south Xiamen, China was 0.988 ± 0.039 ng ml−1. The recoveries of spiked Pb standard in seawater and standard reference water (GBW 08607) were 97.9 and 101.0%, respectively, with a relative standard deviation of 0.98%. This method can be used to determine trace lead concentration in high salt matrix samples, and is especially useful when the eluting peaks do not have a Gaussian-distribution.  相似文献   

14.
Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ30Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ30Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g−1-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice.  相似文献   

15.
Zheng J  Yamada M 《Talanta》2006,68(3):932-939
The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios (235U/238U atom ratio and 234U/238U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise 234U/238U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for 235U/238U atom ratio and lower than 2.0% R.S.D. for 234U/238U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.  相似文献   

16.
Determination of copper using inductively coupled plasma mass spectrometry (ICP-MS) suffers from polyatomic overlays originating from Na+ and Mg2+ matrix elements due to the formation of 40Ar23Na+ and 40Ar25Mg+ in the mass-to-charge ratios of 63 and 65, respectively. The collision/reaction cell technology belongs to the most modern methods used to overcome polyatomic interferences. Gas-filled collision/reaction cell can cause an additional mass bias effect influencing analytical precision of the method. In this study, the additional mass bias effect of the hexapole collision/reaction cell ICP-MS was studied on an example of n(65Cu)/n(63Cu) isotope ratio. As a result, a method for suppressing polyatomic interference on the mass-to-charge ratio of 63 and 65 was introduced and additional mass bias of the collision/reaction cell was lowered to an acceptable level.  相似文献   

17.
A novel method, combining isotope dilution with standard additions, was developed for the analysis of eight elements (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) in seawater. The method requires just 12 mL of sample and employs an off-line pre-concentration step using the commercially available chelating resin Toyopearl AF-Chelate-650M prior to determination by high resolution inductively coupled plasma magnetic sector mass spectrometry (ICP-MS). Acidified samples were spiked with a multi-element standard of six isotopes (57Fe, 62Ni, 65Cu, 68Zn, 111Cd and 207Pb) enriched over natural abundance. In addition, standard additions of a mixed Co and Mn standard were performed on sub-sets of the same sample. All samples were irradiated using a low power (119 mW cm−2; 254 nm) UV system, to destroy organic ligands, before pre-concentration and extraction from the seawater matrix. Ammonium acetate was used to raise the pH of the 12 mL sub-samples (off-line) to pH 6.4 ± 0.2 prior to loading onto the chelating resin. The extracted metals were eluted using 1.0 M Q-HNO3 and determined using ICP-MS. The method was verified through the analysis of certified reference material (NASS-5) and the SAFe inter-comparison samples (S1 and D2), the results of which are in good agreement with the certified and reported consensus values. We also present vertical profiles of the eight metals taken from the Bermuda Atlantic Time Series (BATS) station collected during the GEOTRACES inter-comparison cruise in June 2008.  相似文献   

18.
A species-specific isotope dilution technique for accurate determination of sulfur species in low- and high-boiling petroleum products was developed by coupling capillary gas chromatography with quadrupole ICP-MS (GC-ICP-IDMS). For the isotope dilution step 34S-labeled thiophene, dibenzothiophene, and mixed dibenzothiophene/4-methyldibenzothiophene spike compounds were synthesized on the milligram scale from elemental 34S-enriched sulfur. Thiophene was determined in gasoline, ‘sulfur-free’ gasoline, and naphtha. By analyzing reference material NIST SRM 2296, the accuracy of species-specific GC-ICP-IDMS was demonstrated by an excellent agreement with the certified value. The detection limit is always limited by the background noise of the isotope chromatograms and was determined for thiophene to be 7 pg absolute, which corresponds to 7 ng sulfur/g sample under the experimental conditions used. Dibenzothiophene and 4-methyldibenzothiophene were determined in different high-boiling petroleum products like gas oil, diesel fuel, and heating oil. In this case a large concentration range from about < 0.04 to more than 2,000 μg g−1 was covered for both sulfur species. By parallel GC-ICP-MS and GC-EI-MS experiments (EI-MS electron impact ionization mass spectrometry) the substantial influence of co-eluting hydrocarbons on the ICP-MS sulfur signal was demonstrated, which can significantly affect results obtained by external calibration but not those by the isotope dilution technique.  相似文献   

19.
A new technique to measure 234U/238U and 236U/238U isotope ratios for individual particles in environmental samples was developed, which was a combination of particle isolation under scanning electron microscope (SEM) and secondary ion mass spectrometry (SIMS). The technique was verified by measuring 234U/238U and 236U/238U isotope ratios in individual particles in a simulated environmental sample containing uranium standard (NBL CRM U010) and Pb metal particles. When the uranium particles were not isolated, the relative deviations of the measured isotope ratios from the reference values increased with increasing the signal intensity ratio of 208Pb to 238U, which was due to the molecular ion interferences by the Pb particles co-existing in the sputtered area. By the isolation of individual uranium particles, the interferences were eliminated and the measured isotope ratios were in good agreement with the reference values. The maximum relative deviations among 20 particles were 8.9% for 234U/238U and 13.1% for 236U/238U isotope ratios, respectively. The technique was also successfully applied to the analysis of a real swipe sample containing various kinds of elements.  相似文献   

20.
The ability of a quadrupole-based ICP-MS with an octopole collision cell to obtain precise and accurate measurements of isotope ratios of magnesium, calcium and potassium was evaluated. Hydrogen and helium were used as collision/reaction gases for ICP-MS isotope ratio measurements of calcium and potassium in order to avoid isobaric interference with the analyte ions from (mainly) argon ions 40Ar+ and argon hydride ions 40Ar1H+. Mass discrimination factors determined for the isotope ratios 25Mg/24Mg, 40Ca/44Ca and 39K/41K under optimized experimental conditions varied between 0.044 and 0.075. The measurement precisions for 25Mg/24Mg, 40Ca/44Ca and 39K/41K were found to be 0.09%, 0.43% and 1.4%, respectively. This analytical method that uses ICP-QMS with a collision cell to obtain isotope ratio measurements of magnesium, calcium and potassium was used in routine mode to characterize biological samples (nutrient solution and small amounts of digested plant samples). The mass spectrometric technique was employed to study the dynamics of nutrient uptake and translocation in barley plants at different root temperatures (10 °C and 20 °C) using enriched stable isotopes (25Mg, 44Ca and 41K) as tracers. For instance, the mass spectrometric results of tracer experiments demonstrated enhanced 25Mg and 44Ca uptake and translocation into shoots at a root temperature of 20 °C 24 h after isotope spiking. In contrast, results obtained from 41K tracer experiments showed the highest 41K contents in plants spiked at a root temperature of 10 °C.  相似文献   

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