Precise Isotope Ratio Measurements Research Articles

Copper isotope delta measurements in high purity materials: CCQM-P213 pilot study

Main textAccurate and precise isotope ratio measurements of heavy elements are playing an increasingly important role in modern analytical sciences and have numerous applications. Today, isotope ratio measurements are typically performed with two principal techniques: thermal ionization mass spectrometry (TIMS) and multiple collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). To obtain accurate results by mass spectrometry, isotopic certified reference materials (iCRMs) are needed for mass bias correction and for the validation of the method used for analysis. Thus, it is of paramount importance to achieve measurement comparability of all data reported, and to assess measurement capability of each CRM producer/National Metrology Institute (NMI). Therefore, the international comparison (CCQM-P213) was performed to assess the analytical capabilities of NMIs for the accurate determination of copper isotope ratio delta values in high purity materials. The study was proposed by the coordinating laboratories National Research Council Canada (NRC), National Institute of Standards and Technology (NIST), Bundesanstalt für Materialforschung und -prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) as an activity of the Isotope Ratio Working Group (IRWG) of the Consultative Committee for Amount of Substance - Metrology in Chemistry and Biology (CCQM). Participants included six NMIs and one designated institute (DI) from the six countries. Although no measurement method was prescribed by the coordinating laboratories, MC-ICP-MS with either standard-sample bracketing (SSB) or combined SSB with internal normalization (C-SSBIN) models for mass bias correction were recommended. Results obtained from the six NMIs and one DI were in good agreement.To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/.The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Proteomics-Compatible Fourier Transform Isotopic Ratio Mass Spectrometry of Polypeptides

Measuring the relative abundances of heavy stable isotopes of the elements C, H, N, and O in proteins is of interest in environmental science, archeology, zoology, medicine, and other fields. The isotopic abundance measurements of the fine structure of immonium ions with ultrahigh resolution mass spectrometry obtained in gas-phase fragmentation of polypeptides have previously uncovered anomalous deuterium enrichment in (hydroxy)proline of bone collagen in marine mammals. Here, we provide a detailed description and validation of this approach and demonstrate per mil-range precision of isotopic ratio measurements in aliphatic residues from proteins and cell lysates. The analysis consists of proteomics-type experiment demanding sub-microgram amounts of a protein sample and providing concomitantly protein sequence data allowing one to verify sample purity and establish its identity. A novel software tool protein amino acid-resolved isotopic ratio mass spectrometry (PAIR-MS) is presented for extracting isotopic ratio data from the raw data files acquired on an Orbitrap mass spectrometer.

Evaluation of plasma condition, concentration effect, position effect, and nickel-doping method on non-matrix-matched Fe isotopic analysis by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry

This study investigated the influences of plasma condition, concentration effect, ablation position and on-line addition of an aqueous Ni standard for non-matrix-matched Fe isotopic analysis by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fs LA–MC–ICP–MS). Deviations up to ~0.7‰ in δ56Fe values caused by non-matrix-matched analyses were difficult to eliminate under dry plasma condition even with fs-LA. However, the nebulized water after the ablation cell efficiently reduces or eliminates the matrix-dependent fractionation of Fe isotopes without reducing signal intensity. Furthermore, concentration- and position-dependent fractionation of Fe isotopes was not observed under wet plasma condition. For instrumental mass bias correction, the standard–sample bracketing (SSB) method and SSB with Ni doping (SSB + Ni) were performed in the presence of nebulized water with fs LA–MC–ICP–MS. Results indicate that both the SSB and SSB + Ni methods are sufficient to correct for instrumental mass bias under wet plasma condition, with the SSB + Ni method being more effective in calibrating short-term fluctuations in mass bias with improved external reproducibility of ~0.15‰ (2SD) for δ56Fe values. Compared to SN–MC–ICP–MS, deteriorated precision offered by fs LA–MC–ICP–MS may represent a major limitation for some applications relying upon precise Fe isotope ratio measurements. This approach for non-matrix-matched analysis of Fe isotopes by fs LA–MC–ICP–MS under wet plasma condition combined with the SSB + Ni method allows for more flexibility in tracing detailed geological processes with large Fe isotope fractionation of a wide range of solids. Relatively precise and accurate Fe isotopic compositions of potential reference materials of Balmat pyrite (δ56Fe = −1.32 ± 0.12‰, δ57Fe = −1.91 ± 0.20‰; 2SD, n = 166) and PZH12–24 ilmenite (δ56Fe = −0.38 ± 0.15‰, δ57Fe = −0.57 ± 0.23‰; 2SD, n = 134) were obtained using this analytical protocol, consistent with reference values obtained by solution nebulization (SN)–MC–ICP–MS within analytical uncertainties (Balmat pyrite: δ56Fe = −1.30 ± 0.04‰, δ57Fe = −1.94 ± 0.07‰, 2SD, n = 3; PZH12–24 ilmenite: δ56Fe = −0.38 ± 0.06‰, δ57Fe = −0.55 ± 0.07‰, 2SD, n = 6).

Gd matrix effects on Eu isotope fractionation using MC-ICP-MS: Optimizing europium isotope ratio measurements in geological rock samples

Europium (Eu) has only two isotopes (151Eu and 153Eu). As sequential rare earth elements, Eu and Gd do not easily separate from each other during column chromatography, making it difficult to measure accurate and precise Eu isotope ratio during mass spectral analysis. Eu isotope ratios can be determined by MC-ICP-MS using internal Sm or Gd spikes to correct for mass discrimination. In this report, we discuss and propose optimal conditions for precise and accurate Eu isotope ratio measurements in geological materials (igneous rock samples) using MC-ICP-MS. The NIST3117a ultrapure chemical reagent showed almost no Eu isotope fractionation regardless of the kind of isotope pair used in normalization. A pure Eu fraction with almost no Gd matrix extracted from rock samples also showed nearly the same degree of Eu isotope fractionation regardless of the isotope pair used in normalization. In the case of Eu fraction extracted from highly fractionated granite and high silica volcanic rocks, when 154Gd interference relative to the internal 154Sm standard exceeded ca. 0.1% (due to incomplete Eu separation), this Gd matrix effect created artifactual variation in Eu isotope ratios during MC-ICP-MS analysis. In order to obtain the best estimates of Eu isotope fractionation in geological samples, especially high silica rocks, our analytical methods require complete Eu separation without Gd matrix during sample preparation.

Precise measurement of 234U/238U, 235U/238U and 236U/238U isotope ratios in Fukushima soils using thermal ionization mass spectrometry

Precise and accurate isotope ratio measurements of 234U/238U, 235U/238U and 236U/238U were performed simultaneously in Fukushima contaminated soil samples using thermal ionization mass spectrometry (TIMS). 234U, 235U and 236U isotopes were measured by Daly ion counting system whereas 238U was measured by Faraday collector using mass peak jumping method. Fukushima radio‑cesium contaminated soil samples were digested using microwave oven for complete decomposition. A combined AER-UTEVA separation scheme was applied for purification of U and its accurate isotope ratios measurement in Fukushima soils rich with Fe. Analytical validation of the modified U separation method was tested with certified reference material (CRM) JSd-2. The analytical precision (RSD%) of 234U/238U, 235U/238U and 236U/238U isotope ratios obtained by long-term repeatability for CRM NBL U010 was 0.288% (2σ), 0.017% (2σ) and 0.235% (2σ), respectively. Validation of accurate U isotope ratios measurement was checked with a CRM IRMM-184. This procedure was applied successfully to CRM JSd-2, SRM NIST 4354 and Fukushima soil samples. The concentration of 236U in Fukushima contaminated soils varied from 21.7–194.7 fg/g which showed the mixing effect of global fallout and Fukushima Dai-ichi Nuclear Power Station (FDNPS) accident fallout.

Isotopic analysis of sub‐nanogram neodymium loads using new ATONA™ amplifiers

Emerging research in the geological and nuclear forensics fields demands increasing analytical precision of isotope ratio measurements with decreasing sample sizes. Here we demonstrate the capability of a newly developed amplification technology to make precise neodymium (Nd) isotopic measurements on 100-pg standard loads. The reference materials were analyzed as NdO+ to increase the ionization efficiency of the small analyte loads. The Nd isotopic measurements were made using an IsotopX Isoprobe-T thermal ionization mass spectrometer upgraded with the ATONA™ amplifier system. The ATONA™ amplifier system uses capacitance-based amplification as opposed to traditional impedance-based amplification. The long-term gains of the ATONA™ amplifiers are shown to have less than 1 ppm variability. Repeat measurements of the JNdi-1 reference material demonstrate the ability of the ATONA™ amplification technology to make measurements of 143 Nd/144 Nd ratios with 23 ppm external reproducibility on 100-pg loads. The effect of increasing integration time on analytical reproducibility is also displayed as increasing integration time from 10 to 30 s reduced the external measurement uncertainty from 37 to 23 ppm. These measurements represent an improvement of more than a factor of 3 in external measurement reproducibility relative to previously published 143 Nd/144 Nd measurements of 100-pg loads. This new technology will allow for the measurement of smaller samples for precise isotope ratios and open new avenues of research in the geological and nuclear forensic communities.

Evaluation of the powering modes and geometries of the Liquid Sampling – Atmospheric Pressure Glow Discharge – Orbitrap system for analytical performance and isotope ratio analysis

The liquid sampling atmospheric pressure glow discharge (LS-APGD) microplasma has shown promise in the fields of optical emission spectroscopy and mass spectrometry. In terms of mass spectrometry, it has allowed use of instruments normally applied in “organic” mass spectrometry, to be used for elemental/isotopic applications. The LS-APGD/Orbitrap combination is a particularly attractive alternative to traditional elemental MS systems due to its ability to perform ultra-high-resolution analyses, eliminating isobaric interferences which typically require extensive chemical separation prior to analysis. The LS-APGD has the ability to operate using four different powering modes; solution grounded cathode (SGC), solution grounded anode (SGA), solution powered cathode (SPC), and solution powered anode (SPA). To investigate the utility of each powering mode, the elemental responses and isotope ratio performance were assessed for the pertinent operating parameters (discharge current, solution flow rate, gas flow rate, and inter-electrode displacement). Experiments were performed using a 500 ng mL−1 multielement solution containing Rb, Ag, Ba, Tl, and U. Measurements of 235U/238U were performed using a 200 ng mL−1 solution of CRM-129a. Ultimately, it was determined that the SGC mode showed the best performance in terms of elemental intensity, accuracy, and precision for isotope ratio measurements. The optimal electrode configuration consists of the solution electrode in line with the ion-sampling orifice of the MS, with the counter electrode oriented perpendicular to that axis.

Characterization of the new isotopic reference materials IRMM-524A and ERM-AE143 for Fe and Mg isotopic analysis of geological and biological samples

Isotopic reference materials (IRMs) are crucial for securing accurate and precise isotope ratio measurements of non-traditional stable isotopic systems and for enabling comparison of isotope ratio data obtained at different labs.

High-Sensitivity Measurement of Cr Isotopes by Double Spike MC-ICP-MS at the 10 ng Level.

High-sensitivity and high-precision (2 SD ≤ 0.06‰) measurement of chromium (Cr) isotopes at the 10 ng level was successfully carried out using double spike multiple-collector inductively couple plasma mass spectrometry (MC-ICP-MS). To enhance the signal sensitivity and stability, the Aridus II desolvating nebulizer system was improved by placing its waste gas trap bottle in an ice chamber (5 °C cold trap). This setup, beyond Cr isotope analysis, can be applied to most heavy metal isotope measurements. The sensitivity of the 52Cr signal is ≥300 V mg-1 L (with a 1011Ω amplifier and a 110 μL min-1 uptake rate), an enhancement of ≥1.5 times compared to the Aridus II without the cold trap. In addition, the relative standard deviation of the 52Cr signal varied ≤4% over 8 h, demonstrating high stability. The δ53Cr values of common geological reference materials determined using 10 ng of Cr are in excellent agreement with results measured at 25 ng and 50 ng and are consistent with previous determinations, validating the accurate and precise Cr isotope ratio measurements. An empirical method is proposed to correct for the residual (after subtraction) effect of Fe interference on δ53Cr determination. This method relies on a linear relationship between the [Fe]/[Cr] and δ53Cr shift within one analytical session. Finally, we report the δ53Cr values of 19 new reference materials, ranging from -0.44‰ to 0.49‰. Among them, GSS-7 (-0.44 ± 0.02‰, 2 SD, n = 5), GSS-4 (0.48 ± 0.02‰, 2 SD, n = 5), and GSD-10 (0.49 ± 0.05‰, 2 SD, n = 5) can be used as candidate reference materials for interlaboratory comparisons to complement existing ones that are mostly isotopically unfractionated from the bulk silicate earth.

Correction of Mass Spectrometric Interferences for Rapid and Precise Isotope Ratio Measurements of Calcium from Biological Samples Using ICP-Mass Spectrometry.

Stable isotope compositions of calcium (Ca) provide useful information concerning metabolic alterations of Ca in human and animal bodies. For the measurements of Ca isotope ratio, great care must be taken for the mass spectrometric interferences on Ca isotopes (42Ca+, 43Ca+, and 44Ca+) from doubly charged strontium (Sr) ions (84Sr2+, 86Sr2+, and 88Sr2+). To obtain reliable stable isotope data of Ca, we developed a new correction technique for the mass spectrometric interferences by mSr2+ ions based on standard addition method. Addition of a small fraction of Sr onto a Ca solution shifts the measured Ca isotope ratios on a three-isotope diagram (i.e., δ44Ca and δ43Ca) along a mixing line defined by both the true Ca isotope ratio and the Sr isotope ratio. Therefore, the true Ca isotope ratio of a sample can be obtained as the crossover point of mass dependent fractionation line and the mixing line. With the present correction technique, precise and accurate isotope ratio measurements can be made on analyte solutions having a CSr/CCa ratio (concentration ratio) of 0.03, which is 6 times higher than the CSr/CCa ratio applicable to the conventional correction technique.

Obtaining Accurate Isotopic Compositions with the Double Spike Technique: Practical Considerations

Ever‐increasing precision in isotope ratio measurements requires a concomitant small bias within and between laboratories. The double spike technique is the most suitable method to obtain reliable isotope composition data that are accurately corrected for instrumental mass fractionation. Compared with other methods, such as sample‐calibrator bracketing (SCB), only the double spike technique can correct for all sources of fractionation after equilibration of the sample with the double spike, such as that incurred during chemical separation and measurement. In addition, it is not dependent on a priori assumptions of perfect matrix matching of samples to reference materials or quantitative recovery of the sample through the chemical separation procedure to yield accurate results. In this review article, we present a detailed discussion of the merits of the double spike technique, how to design and calibrate a suitable double spike and analytical strategies. Our objective is to offer a step‐by‐step introduction to the use of the double spike technique in order to lower potential barriers that researchers new to the subject might face, such that double spiking will replace SCB as the measurement method of choice.

Secondary Ion Mass Spectrometry Methodology for Isotopic Ratio Measurement of Micro‐Grains in Thin Sections: True Grain Size Estimation and Deconvolution of Inter‐Grain Size Gradients and Intra‐Grain Radial Gradients

In a thin section, grains that were approximately spherical in situ appear circular in cross section, and the distribution of apparent diameters frequently assumed to be their size distribution. Scanning ion imaging by secondary ion mass spectrometry (SIMS) is capable of providing precise (< 1‰) stable isotope ratio measurements of such grains, but, importantly, also registers their rate of evolution in apparent size as they are ablated by the primary beam. By assessing rates of radius change with depth, the described methodology enables the ‘true’ size of grains to be estimated, as well as the distance of the sectioned surface from the original grain centre. Transects in three dimensions are made possible, and this capability enables better identification (and thus separation) of both inter‐grain chemical signatures as a function of grain size, and intra‐grain radial trends. In this example, we highlight the specific application to pyrite (FeS2) minerals, which are frequently analysed by SIMS to determine their inter‐grain and intra‐grain geochemical variations, particularly in their sulfur stable isotopic ratios (δ34S). Benefits of the new methodology over the Faraday cup ‘spot mode’ are described. Data correction algorithms and precision considerations are discussed.

Ultra-trace Cu isotope ratio measurements via multi-collector ICP-mass spectrometry using Ga as internal standard: an approach applicable to micro-samples

The capabilities of Cu isotope ratio measurements are often restricted by the small volumes of sample available and/or their low Cu concentration. In this work, an analytical approach was developed for performing Cu isotopic analysis via multi-collector ICP-mass spectrometry (MC-ICP-MS) at ultra-trace level using Ga as an internal standard for mass bias correction. The minimum concentration of Cu required for accurate and precise isotope ratio measurements was established to be 20 μg L−1 with wet plasma conditions and 5 μg L−1 with dry plasma conditions. The use of Ga as an internal standard for mass bias correction provided several advantages compared to Ni, i.e. improved internal precision on δ65Cu values and lower blank levels. Ga can also be used at a 4-fold lower concentration level than Ni. However, in wet plasma conditions, the signals of 36Ar16O21H+ and 40Ar15N16O+ interfered with the signals of 69Ga+ and 71Ga+, respectively, while in dry plasma conditions, realized by the use of a desolvation unit, 69Ga+ suffered from spectral interference from 40Ar14N21H+. These interferences were resolved by using medium mass resolution. For validation purposes, the approach was applied to commercially available blood and serum samples. The δ65Cu values for the samples measured at a concentration level of 5 μg L−1 Cu and 5 μg L−1 Ga using dry plasma conditions were in good agreement with those obtained for isotope ratio measurements at the “standard” concentration level of 200 μg L−1 Cu and 200 μg L−1 Ni using wet plasma conditions. In addition, the δ65Cu values obtained for micro-samples of serum/blood (volume of 100 µL) were in good agreement with the corresponding ones obtained using the “standard” volume for isotopic analysis (500 μL).

Determination of cadmium in sediments by diluted HCI extraction and isotope dilution ICP-MS

Isotope dilution ICP-MS is proposed to measure the mass fraction of Cd extracted by diluted HCl in marine sediments, using a fast and simple extraction procedure based on ultrasonic probe agitation. The 111Cd isotope was added before the extraction to achieve isotope equilibration with native Cd solubilized from the sample. The parameters affecting trueness and precision of isotope ratio measurements were evaluated carefully and subsequently corrected in order to minimize errors; they were: detector dead time, spectral interferences, mass discrimination factor and optimum sample/spike ratio. The mass fraction of Cd extracted was compared with the sum of the certified contents of the three steps of the sequential extraction procedure of the Standards, Measurements and Testing Programme (SM&T) analysing the BCR 701 sediment to validate the method. The certified and measured values agreed, giving a measured / certified mass fraction ratio of 1.05. Further, the extraction procedure itself was studied by adding the enriched isotope after the extraction step, which allowed verifying that analyte losses occurred during this process. Two additional reference sediments with certified total cadmium contents were also analysed. The method provided very good precision (0.9%, RSD) and a low detection limit, 1.8 ng g−1. The procedural uncertainty budget was estimated following the EURACHEM Guide by means of the ‘GUM Workbench’ software, obtaining a relative expanded uncertainty of 1.5%. The procedure was applied to determine the bioaccessible mass fraction of Cd in sediments from two environmentally and economically important areas of Galicia (rias of Arousa and Vigo, NW of Spain).

Anion-Exchange Fibers for Improved Sample Loading in Ultra-Trace Analysis of Plutonium by Thermal Ionization Mass Spectrometry.

A new sample loading procedure was developed for isotope ratio measurements of ultratrace amounts of plutonium with thermal ionization mass spectrometry (TIMS). The goal was to determine the efficacy of a polymer fiber architecture for TIMS sample loading by following similar sample loading procedures as those used in bead loading. Fibers with diameter of approximately 100 μm were prepared from triethylamine-quaternized-poly(vinylbenzyl chloride) cross-linked with diazabicyclo[2.2.2]octane. Fiber sections (2.5 mm) were loaded with 10 pg of New Brunswick Laboratory certified reference material (NBL CRM) 128 from an 8 M HNO3 matrix and affixed to rhenium filaments with collodion. A single filament assembly was used for these analyses. Total ion counts (239Pu + 242Pu) and isotope ratios obtained from fiber-loaded filaments were compared to those measured by depositing Pu amended resin beads on the filament. Fiber loading was found to improve sensitivity, accuracy, and precision of isotope ratio measurements of plutonium when compared to the established resin bead loading method, while maintaining its simplicity. The average number of detected Pu+ counts was 180% greater, and there was a 72% reduction in standard deviation of ratio measurements when using fiber loading. An average deviation of 0.0012 (0.117%) from the certified isotope ratio value of NBL CRM Pu128 was measured when fiber loading versus a deviation of 0.0028 (0.284%) when bead loading. The fiber formation method presented in this study can be extended to other anion-exchange polymer chemistries and, therefore, offers a convenient platform to investigate the efficacy of novel polymer chemistries in sample loading for TIMS.

Studies on Isotope Ratio Measurement of Cl by Inductively Coupled Plasma Triple-quad Mass Spectrometry.

Fundamental studies on isotope ratio measurement of Cl were carried out using inductively coupled plasma triple-quad mass spectrometry (ICP-MS/MS) and the analytical performance obtained was compared to that obtained by ICP sector field mass spectrometer (ICP-SFMS). Though the polyatomic ion interferences of 16O18O1H and 36Ar1H with respect to 35Cl and 37Cl, respectively, made a negative effect on the accuracy and the precision for isotope ratio measurements of Cl, the ICP-SFMS could eliminate these interferences by medium mass resolution mode (m/Δm = 4000) and achieved the isotope ratio measurements with 0.2 - 0.5% of relative standard deviation (RSD) at the concentrations of Cl from 1 to 10 mg kg-1. In the case of ICP-MS/MS, both the single-MS mode without collision reaction gas and the MS/MS mode with collision reaction gases such as oxygen (O2) and hydrogen (H2) were examined and compared their analytical sensitivities as well as the precisions of isotope ratio measurement of Cl. The precisions of Cl isotope ratio measurements were 3 - 14% of RSD at the concentrations of Cl from 5 to 100 mg kg-1, when single-MS mode was carried out, even though the similar isotope ratios of 35Cl/37Cl could be obtained. In the case of O2 gas for MS/MS mode with mass-shift method, precisions of 0.3 - 2% of RSD were obtained at the concentration range of 1 - 100 mg kg-1. In the case of H2 gas, similar sensitivities as those obtained by ICP-SFMS and the precisions of 0.2 - 0.5% of RSD at the concentration range of 1 - 10 mg kg-1 were obtained. From these results, it was evaluated that the ICP-MS/MS in MS/MS mode with collision reaction gas could be used for Cl isotope ratio measurements for such studies as stable isotope tracers, isotope abundance measurements in nuclear chemistry and accurate determinations by isotope dilution mass spectrometry.

Integrated Extraction Chromatographic Separation of the Lithophile Elements Involved in Long-Lived Radiogenic Isotope Systems (Rb-Sr, U-Th-Pb, Sm-Nd, La-Ce, and Lu-Hf) Useful in Geochemical and Environmental Sciences.

A fast and efficient sample preparation method in view of isotope ratio measurements is described, allowing the separation of 11 elements involved, either as "parent" or as "daughter" isotopes, in six radiogenic isotope systems used as chronometers and tracers in earth, planetary, and environmental sciences. The protocol is based on small extraction chromatographic columns, used either alone or in tandem, through which a single nitric acid solution is passed, without any intervening evaporation step. The columns use commercially available extraction resins (Sr resin, TRU resin, Ln resin, RE resin, and again Ln resin for isolating Sr and Pb, LREE then La-Ce-Nd-Sm, Lu(Yb), and Hf, Th, and U, respectively) along with an additional, in-house prepared resin for separating Rb. A simplified scheme is proposed for samples requiring the separation of Sr, Pb, Nd, and Hf only. Adverse effects of troublesome major elements (Fe3+, Ti) are circumvented by masking with ascorbic acid and hydrofluoric acid, respectively. Typical recoveries in the 85-95% range are achieved, with procedural blanks of 10-100 pg, negligible with regard to the amounts of analytes processed. The fractions separated are suitable for high precision isotope ratio measurements by TIMS or MC-ICP-MS, as demonstrated by the repeat analyses of several international reference materials of basaltic composition for 87Sr/86Sr, 208,207,206Pb/204Pb, 143Nd/144Nd, 176Hf/177Hf, and 230Th/232Th. Concentration data could be obtained by spiking and equilibrating the sample with appropriate isotopic tracers before the onset of the separation process and, finally, measuring the isotope ratios modified by the isotope dilution process.

Measurement and validation of uranium isotope ratio in uranium ore for isotopic fingerprinting

Accurate determination of uranium isotope ratio can act as an efficient fingerprint in the nuclear forensics to identify source and intended use of illicit trafficking of uranium material. In this context, a rapid chemical separation technique to isolate uranium from uranium ore sample was developed using commercial extraction chromatographic resin. Uranium isotope ratio was measured using thermal ionization mass spectrometry (TIMS). Standard reference material (NBS U010) was used for validating the accuracy and precision of isotope ratio measurement by TIMS. The method is successfully applied to a natural ore (uraninite ore) for the determination of naturally occurring uranium isotope ratio.

Contrasting particle size distributions and Fe isotope fractionations during nanosecond and femtosecond laser ablation of Fe minerals: Implications for LA-MC-ICP-MS analysis of stable isotopes

Laser ablation coupled to a multi-collector inductively coupled mass spectrometer (LA-MC-ICP-MS) is a promising tool for in situ analysis of metal and metalloid stable isotope ratios. Potential isotopic fractionation associated with laser ablation may, however, cause biased sampling of the substrate, posing a major challenge for precise and accurate isotope ratio measurements. To better characterize the nature of laser ablation induced isotopic fractionation, this study compared particle morphologies, sizes, and size-dependent Fe isotope fractionations produced by ablation of a suite of semi-conductive samples, including natural Fe oxide, sulfide, and carbonate minerals, under various conditions using a 193nm ArF nanosecond (ns) laser and a 266nm Ti:sapphire femtosecond (fs) laser. Ablation-produced particles were sorted based on aerodynamic size using a cascade impactor, and Fe isotope compositions of size-sorted particles were then measured offline using conventional solution nebulization ICP-MS to quantify isotopic fractionation produced by the laser ablation. Particle morphology and size distributions produced by ns-laser ablation are more substrate and fluence dependent as compared to fs-laser ablation, resulting from the thermal nature of ns-laser ablation. Often, a higher proportion of the ablated Fe mass resides in particles with large aerodynamic sizes during ns-laser ablation as compared to fs-laser ablation, posing a potential difficulty for LA-ICP-MS analysis due to the increased possibility of incomplete ionization of large particles. Significant size-dependent Fe isotope fractionations of up to several per mil can occur during both ns- and fs-laser ablation, highlighting the importance of quantitative transport of particles to the ICP-MS for accurate Fe isotope analysis. Size-dependent Fe isotope fractionation observed for fs-laser ablation of all Fe minerals can be explained by particle formation through a condensation model, but multiple processes need to be considered to explain the observed Fe isotope fractionation during ns-laser ablation. Mass-balance calculations suggest that ns-laser ablation does not sample magnetite stoichiometrically for Fe isotope compositions at low fluence (1J/cm2), but does at higher fluences for all minerals. In contrast, fs-laser ablation always provides stoichiometric sampling for Fe isotopes regardless of fluence. Results of this study demonstrate that ns-laser ablation is substrate- and fluence-dependent, resulting in variable particle size distributions and Fe isotope fractionations, and possible non-stoichiometric sampling of semi-conductive samples for Fe isotope analysis. Instead, fs-laser ablation largely minimizes the substrate and fluence dependence, providing more consistent ablation.

High resolution isotopic analysis of U-bearing particles via fusion of SIMS and EDS images

The result of fusing energy-dispersive X-ray spectroscopy (EDS) and secondary ion mass spectrometry (SIMS) images of U-bearing particles.