A rapid method for uranium isotope ratio measurement by inductively coupled plasma mass spectrometry

Uranium isotope ratio U 234/238 can be measured by commercial high-performance inductively coupled plasma mass spectrometry (ICP-MS) with good precision and accuracy (relative standard deviation RSD<2%). The method is based on acquiring the data using a peak jump mode and a collecting signal 10 times longer for low abundance isotopes. Uranium isotope standards U-005 to U-200 from the National Bureau of Standards (NBS) were used for method development. The optimum uranium concentration range for analysis for dissolved samples is from 50 to 200 g l^–1.     

Determination of uranium in marine sediment pore waters by isotope dilution inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) was used in an isotope dilution mode to assay small-volume (0.25 ml) sediment pore waters for their uranium contents, using ²³⁶U as the spike. The only pretreatment required was a simple dilution by a factor of 20, which gave sufficient volume for three replicate analyses per sample. Rapid and accurate results were obtained for a variety of samples and standards, ranging in concentration from 0.05 to 10 ng U ml^?1. A suite of 30 samples can be analysed in less than 6 h by this method. The relative standard deviation was better than 1.9%, with a detection limit, based on 3σ background, of 2 pg U ml^?1 in solution (40 pg ml^?1 in samples). Sea water is a difficult matrix for ICP-MS and thus the method is generally suitable for uranium determinations in many other sample solutions.     

Precise isotope ratio measurements for uranium, thorium and plutonium by quadrupole-based inductively coupled plasma mass spectrometry

Precise long-term measurements of uranium and thorium isotope ratios was carried out in 1 μg/L solutions using a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS). The isotopic ratios of uranium (²³⁵U/ ²³⁸U = 1, 0.02 and 0.00725) were determined using a cross-flow nebulizer (CFN, at solution uptake rate of 1 mL/min) and a low-flow microconcentric nebulizer (MCN, at solution uptake rate of 0.2 mL/min) over 20 h. For 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) relative external standard deviations (RESDs) of 0.05% and 0.044% using CFN and MCN, respectively, can be achieved. Additional short term isotope ratio measurements using a direct injection high-efficiency nebulizer (DIHEN) of 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) at a solution uptake rate of 0.1 mL/min yielded an RSD of 0.06–0.08%. The sensitivity of solution introduction by DIHEN for uranium, thorium and plutonium (145 MHz/ppm, 150 MHz/ppm and 177 MHz/ppm, respectively) increased significantly compared to CFN and MCN and the solution uptake rate can be reduced to 1 μL/ min in DIHEN-ICP-MS. Isotope ratio measurements at an ultralow concentration level (e.g. determination of ²⁴⁰Pu/ ²³⁹Pu isotope ratio in a 10 ng/L Pu waste solution) were carried out for the characterization of radioactive waste and environmental samples.     

Precise isotope ratio measurements for uranium, thorium and plutonium by quadrupole-based inductively coupled plasma mass spectrometry

Precise long-term measurements of uranium and thorium isotope ratios was carried out in 1 μg/L solutions using a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS). The isotopic ratios of uranium (²³⁵U/ ²³⁸U = 1, 0.02 and 0.00725) were determined using a cross-flow nebulizer (CFN, at solution uptake rate of 1 mL/min) and a low-flow microconcentric nebulizer (MCN, at solution uptake rate of 0.2 mL/min) over 20 h. For 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) relative external standard deviations (RESDs) of 0.05% and 0.044% using CFN and MCN, respectively, can be achieved. Additional short term isotope ratio measurements using a direct injection high-efficiency nebulizer (DIHEN) of 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) at a solution uptake rate of 0.1 mL/min yielded an RSD of 0.06–0.08%. The sensitivity of solution introduction by DIHEN for uranium, thorium and plutonium (145 MHz/ppm, 150 MHz/ppm and 177 MHz/ppm, respectively) increased significantly compared to CFN and MCN and the solution uptake rate can be reduced to 1 μL/ min in DIHEN-ICP-MS. Isotope ratio measurements at an ultralow concentration level (e.g. determination of ²⁴⁰Pu/ ²³⁹Pu isotope ratio in a 10 ng/L Pu waste solution) were carried out for the characterization of radioactive waste and environmental samples. Received: 1 December 1998 / Revised: 25 January 1999 / Accepted: 31 January 1999     

Application of laser ablation inductively coupled plasma mass spectrometry for the isotopic analysis of single uranium particles

The paper describes the application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the isotopic analysis of individual uranium-oxide particles. The procedure developed is suitable for the accurate measurement of ²³⁴U, ²³⁵U, ²³⁶U and ²³⁸U isotopes in single actinide particles with lateral dimensions down to 10 μm. The ²³⁵U/²³⁸U isotope ratios can be obtained with a precision of a few percent relative standard deviation using a single collector ICP-MS instrument. The precision could be improved by the use of slow ablation and by taking several LA-ICP-MS replicate spectra on the same particle investigated. For the minor isotopes use of higher mass resolution (R = 4000) was necessary in some cases to avoid spectral interferences. The technique developed offers a rapid and accurate possibility for the isotopic composition determination of uranium-containing individual particles in environmental and safeguards samples.     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS)

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)₂, and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is ±0.07‰ on δ⁵⁶Fe and ±0.09‰ on δ⁵⁷Fe while typical internal precision of a measurement (1S.E.) is ±0.03‰ on δ⁵⁶Fe and ±0.04‰ on δ⁵⁷Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of ∼2 nmol L⁻¹ for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L⁻¹ Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. δ⁵⁶Fe varies between −3.5‰ and +1.5‰. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.     

电感耦合等离子体质谱(ICP-MS)法测定水产品中锶同位素比值

为推动锶同位素在水产品溯源中的应用,本文建立了基于电感耦合等离子体质谱法（ICP-MS）测定水产品中锶同位素比值的分析方法。水产品组织经冻干研磨和微波消解后,用ICP-MS测定样品溶液中的锶同位素比值,并采用标准品-样品-标准品交叉测量方法降低质量歧视效应的影响。结果表明,通过稀释样品消解溶液,将总锶浓度控制在70-100 μg/L,并与80 μg/L的锶同位素标准品溶液进行交叉测量,可准确校正质量歧视效应;84Sr/86Sr、87Sr/86Sr和88Sr/86Sr的日内精密度分别为0.06%、0.03%和0.03%,日间精密度分别为0.08%、0.04%和0.03%;按照所建立的方法测定大虾和扇贝生物成分分析标准物质的锶同位素比值,84Sr/86Sr、87Sr/86Sr和88Sr/86Sr的相对标准偏差均低于0.1%。该方法前处理简单快捷并且测量精密度高,可为锶同位素比值测定并进一步应用于水产品溯源研究提供技术支撑。     

Determination of barium in marine waters by isotope dilution inductively coupled plasma mass spectrometry

A simple and accurate method is presented for determining barium in marine waters. Equal amounts of an enriched isotope spike and sample are diluted 100-fold with 1% nitric acid. The diluted sample is introduced into an inductively coupled plasma mass spectrometer with a peristaltic pump and the mass region from 135 to 138 is scanned 480 times. The entire procedure takes less than 10 min per sample and is accurate to better than 1% as determined by intercalibration with isotope dilution mass spectrometry.     

Trace enrichment and measurement of platinum by flow injection inductively coupled plasma mass spectrometry

A flow injection system incorporating an alumina microcolumn has been coupled to inductively coupled plasma mass spectrometry (ICP-MS) for on-line preconcentration and determination of platinum (IV) in natural waters. Depending on the nature of the sample, a nominal preconcentration factor of up to 600 can be achieved by eluting with 50l of 2 mol/l NH₄OH. The limit of detection after a 5 min preconcentration time was 4 ngl^-1, with a relative standard deviation of 4% (100 ngl^-1 working solution). The proposed method was assessed for the determination of platinum (IV) in natural waters, motor car exhaust and some common analytical reagents.     

Trace enrichment and measurement of platinum by flow injection inductively coupled plasma mass spectrometry

A flow injection system incorporating an alumina microcolumn has been coupled to inductively coupled plasma mass spectrometry (ICP-MS) for on-line preconcentration and determination of platinum (IV) in natural waters. Depending on the nature of the sample, a nominal preconcentration factor of up to 600 can be achieved by eluting with 50microl of 2 mol/l NH(4)OH. The limit of detection after a 5 min preconcentration time was 4 ngl(-1), with a relative standard deviation of 4% (100 ngl(-1) working solution). The proposed method was assessed for the determination of platinum (IV) in natural waters, motor car exhaust and some common analytical reagents.     

Element fingerprinting of marine organisms by dynamic reaction cell inductively coupled plasma mass spectrometry

A method for the determination of sixteen elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) in seafood by dynamic reaction cell inductively coupled plasma mass spectrometry (ICP–DRC–MS) is presented. A preliminary study of polyatomic interferences was carried out in relation to the chemical composition of marine organisms belonging to different taxa. Acid effects and other matrix effects in marine organisms submitted to closed-vessel microwave digestion were investigated as well. Ammonia was the reactive gas used in the DRC to remove polyatomic ions interfering with ²⁷Al, ⁵²Cr, ⁵⁶Fe and ⁵¹V. Optimal conditions for the simultaneous determination of analytes were identified in order to develop a fast multielement method. A suite of real samples (mussels and various fish species) were used during method development along with three certified reference materials: BCR CRM 278R (mussel tissue), BCR CRM 422 (cod muscle) and DORM-2 (dogfish muscle). The proposed analytical approach can be used in conjunction with suitable chemometric procedures to address quality and safety issues in aquaculture and fisheries. As an example, a case study is described in which mussels from three farming sites in the Venice Lagoon were distinguished by multivariate analysis of element fingerprints.      

Isotope ratio determinations by inductively coupled plasma/mass spectrometry for zinc bioavailability studies

A method is described for the measurement of ⁶⁷Zn/^6*Zn and ⁷⁰ZN/⁶⁸Zn ratios by inductively coupled plasma/mass spectrometry with ultrasonic nebulization. The method provides sufficient accuracy and precision for zinc bioavailability studies that use samples of human feces or blood plasma. Extraction of zinc from ashed samples yields aqueous solutions sufficiently devoid of matrix ions that could affect count rates and isotope ratios. Effects of sodium matrix, zinc concentration, and instrumental parameters on the precision of isotope ratio determinations are documented. Additions of spikes enriched in ⁶⁷Zn and ⁷⁰Zn to natural-abundance fecal samples verify that ratios can be determined on solutions 30 μM in zinc (<300 nmol of zinc per sample) with relative accuracies of <1% and relative standard deviations (r.s.d.) of ?1% over the range from natural abundance to 370 atom% excess of ⁷⁰Zn and to 84 atom% excess of ⁶⁷Zn.     

Determination of metals in marine species by microwave digestion and inductively coupled plasma mass spectrometry analysis

A microwave digestion method suitable for determination of multiple elements in marine species was developed, with the use of cold vapor atomic spectrometry for the detection of Hg, and inductively coupled plasma mass spectrometry for all of the other elements. An optimized reagent mixture composed of 2 ml of HNO₃, 2 ml of H₂O₂ and 0.3 ml of HF used in microwave digestion of about 0.15 g (dry weight) of sample was found to give the best overall recoveries of metals in two standard reference materials. In the oyster tissue standard reference material (SRM 1566b), recoveries of Na, Al, K, V, Co, Zn, Se, Sr, Ag, Cd, Ni, and Pb were between 90% and 110%; Mg, Mn, Fe, Cu, As, and Ba recoveries were between 85% and 90%; Hg recovery was 81%; and Ca recovery was 64%. In a dogfish certified reference material (DORM-2), the recoveries of Al, Cr, Mn, Se, and Hg were between 90% and 110%; Ni, Cu, Zn, and As recoveries were about 85%; and Fe recovery was 112%. Method detection limits of the elements were established. Metal concentrations in flounder, scup, and blue crab samples collected from coastal locations around Long Island and in the Hudson River estuary were determined.     

A rapid isotope dilution inductively coupled plasma mass spectrometry procedure for uranium bioassay

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.     

Flow-injection technique for determination of uranium and thorium isotopes in urine by inductively coupled plasma mass spectrometry

A sensitive and efficient flow-injection (FI) preconcentration and matrix-separation technique coupled to sector field ICP–mass spectrometry (SF-ICP–MS) has been developed and validated for simultaneous determination of ultra-low levels of uranium (U) and thorium (Th) in human urine. The method is based on selective retention of U and Th from a urine matrix, after microwave digestion, on an extraction chromatographic TRU resin, as an alternative to U/TEVA resin, and their subsequent elution with ammonium oxalate. Using a 10 mL sample, the limits of detection achieved for ²³⁸U and ²³²Th were 0.02 and 0.03 ng L^–1, respectively. The accuracy of the method was checked by spike-recovery measurements. Levels of U and Th in human urine were found to be in the ranges 1.86–5.50 and 0.176–2.35 ng L^–1, respectively, well in agreement with levels considered normal for non-occupationally exposed persons. The precision obtained for five replicate measurements of a urine sample was 2 and 3% for U and Th, respectively. The method also enables on-line measurements of the ²³⁵U/²³⁸U isotope ratios in urine. Precision of 0.82–1.04% (RSD) was obtained for ²³⁵U/²³⁸U at low ng L^–1 levels, using the FI transient signal approach.     

Separation of uranium and plutonium isotopes for measurement by multi collector inductively coupled plasma mass spectroscopy

Uranium (U) and plutonium (Pu) isotopes in coral soils, contaminated by nuclear weapons testing in the northern Marshall Islands, were isolated by ion-exchange chromatography and analyzed by mass spectrometry. The soil samples were spiked with ²³³U and ²⁴²Pu tracers, dissolved in minerals acids, and U and Pu isotopes isolated and purified on commercially available ion-exchange columns. The ion-exchange technique employed a TEVA^® column coupled to a UTEVA^® column. U and Pu isotope fractions were then further isolated using separate elution schemes, and the purified fractions containing U and Pu isotopes analyzed sequentially using multi-collector inductively coupled plasma mass spectrometer (MCICP-MS). High precision measurements of ²³⁴U/²³⁵U, ²³⁸U/²³⁵U, ²³⁶U/²³⁵U, and ²⁴⁰Pu/²³⁹Pu in soil samples were attained using the described methodology and instrumentation, and provide a basis for conducting more detailed assessments of the behavior and transfer of uranium and plutonium in the environment.     

Determination of uranium isotopic composition and 236U content of soil samples and hot particles using inductively coupled plasma mass spectrometry

As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The 236U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. Nuclear track radiography was applied for the identification and extraction of hot radioactive particles from soil samples. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on double-focusing inductively coupled plasma mass spectrometry (DF-ICP-MS) with a MicroMist nebulizer and a direct injection high-efficiency nebulizer (DIHEN). The performance of the DF-ICP-MS with a quartz DIHEN and plasma shielded torch was studied. Overall detection efficiencies of 4 x 10(-4) and 10(-3) counts per atom were achieved for 238U in DF-ICP-QMS with the MicroMist nebulizer and DIHEN, respectively. The rate of formation of uranium hydride ions UH+/U+ was 1.2 x 10(-4) and 1.4 x 10(-4), respectively. The precision of short-term measurements of uranium isotopic ratios (n = 5) in 1 microg L(-1) NBS U-020 standard solution was 0.11% (238U/235U) and 1.4% (236U/238U) using a MicroMist nebulizer and 0.25% (235U/238U) and 1.9% (236U/P38U) using a DIHEN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the 236U/238U ratio ranged from 10(-5) to 10(-3). Results obtained with ICP-MS, alpha- and gamma-spectrometry showed differences in the migration properties of spent uranium, plutonium, and americium. The isotopic ratio of uranium was also measured in hot particles extracted from soil samples.     

Determination of thorium and uranium in activated concrete by inductively coupled plasma mass spectrometry after anion-exchange separation

A sensitive analytical method was established for the determination of Th and U in activated concrete samples. The method combines an anion-exchange separation step with an ICP-MS determination technique. In the ICP-MS measurement, a few μg mL^–1 of Al and Ca, a few ng mL^–1 of Mn, La, Ce, Nd and Pb and pg mL^–1 amounts of Li, Zr, Nb and Ba coexisting in the anion-exchange fraction of Th and U did not interfere. No adverse interference effects were observed in real sample analyses. The obtained detection limits (3σ, n = 10) of Th and U were 2.3 and 1.8 pg mL^–1, respectively. The analytical precisions for ca. 5 μg g^–1 Th and ca. 1 μg g^–1 U in real activated concrete samples were equally less than 7% RSD. The accuracies obtained by the analysis of GSJ rock standard samples were –18.1 to 0.4% for the Th determination and –14.0 to –5.7% for the U determination. The method uses the conventional absolute calibration curve. The internal standard calibration is unnecessary. Received: 14 March 1999 / Revised: 13 July 1999 / Accepted: 15 July 1999