Magnesium isotope ratio measurements by negative thermal ionisation mass spectrometry using molecular fluoride ions

A new technique for accurate Mg isotope ratio measurements has been developed with MgF₂ as sample compound. With the help of a fluorinating agent negatively charged MgF₃ molecular ions were formed in the ion source of a thermal ionisation mass spectrometer. An evaporation study has been performed and the results clearly show that Mg is evaporated from the filament as MgF₂ molecules. The MgF₂ technique has been applied in the certification of a candidate ²⁶Mg-enriched Spike Isotope Reference Material. The result from this new technique has been compared with results obtained for the same material using ICP-MS.     

Osmium isotope ratio measurements by negative thermal ionization mass spectrometry (NTI-MS)

Summary A negative thermal ionization technique using a Faraday cup as detector is presented, which allows precise isotope ratio measurements of osmium. For the major isotopes the relative standard deviation is in the range of 0.004% to 0.07%. Sample amounts down to 1 ng were loaded as hexachloroosmic acid. From the results it is concluded that also sample amounts in the pg range will result in sufficient ion currents of OsO ₃ ^– , avoiding an electron multiplier as detector. H₂OsCl₆ was chosen because this compound is the most suitable chemical form after separation of osmium from geological samples. The introduction of oxygen or freons into the ion source enhances the emission of OsO ₃ ^– ions by a factor of up to more than ten. Ionization efficiencies of more than 30% are obtained by using oxygen. The stability of the ion current is better in the case of oxygen than in the case of freons. However, both compounds are stabilizing the high voltage potentials of the optical ion lenses in the ion source, a permanent problem in NTI-MS. The described isotope ratio measurement is an important improvement for Re/Os dating of terrestrial and extraterrestrial samples.     

Matrix effects in plutonium isotope ratio measurements using thermal ionization mass spectrometry

Journal of Radioanalytical and Nuclear Chemistry - Through high fidelity measurements of four different plutonium certified reference material standards from New Brunswick Laboratory, the mass...     

Identification of ground water contaminations by landfills using precise boron isotope ratio measurements with negative thermal ionization mass spectrometry

 Precise boron isotope ratio measurements with negative thermal ionization mass spectrometry were used for the identification of ground water contaminations by leakages of landfills. BO^- ₂thermal ions were produced to determine the ¹¹B/¹⁰B isotope ratio, which was expressed as δ¹¹B value in ‰ normalized to the standard reference material NIST SRM 951. For example, household waste influences the boron isotope ratio by specific components such as washing powder. In the case of one investigated landfill low δ¹¹B values correlate well with high boron concentrations in contaminated seepage water samples and vice versa for uncontaminated ground water samples. Possible boron contributions of rainwater were taken into account, determining a boron content of 2.3 μg/L and a δ¹¹B value of 13.1‰ for a representative sample. Such low boron concentrations were determined by isotope dilution mass spectrometry (detection limit 0.3 μg/L) whereas higher contents were also analyzed by a spectrophotometric method. However, different sources of contamination could only be identified by the isotope ratio and not by the concentration of boron. Received: 9 December 1996/Accepted: 18 February 1997     

Determination of K-factors for isotope abundance measurements of uranium and plutonium by thermal ionisation mass spectrometry

K-factors (= certified isotope ratio/observed isotope ratio) are determined for the isotope abundance measurements of uranium and plutonium by thermal ionisation mass spectrometry. An mdf of 0.07% and 0.18% per mass unit differing by a factor of about 3, is obtained for uranium and plutonium, respectively, employing double rhenium filament assembly in the ion source and Faraday cup as the detector using the presently available isotopic reference materials of uranium and plutonium.     

Carbon isotope ratio measurements of glyphosate and AMPA by liquid chromatography coupled to isotope ratio mass spectrometry

The interest in compound-specific isotope analysis for product authenticity control and source differentiation in environmental sciences has grown rapidly during the last decade. However, the isotopic analysis of very polar analytes is a challenging task due to the lack of suitable chromatographic separation techniques which can be used coupled to isotope ratio mass spectrometry. In this work, we present the first method to measure carbon isotope compositions of the widely applied herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA) by liquid chromatography coupled to isotope ratio mass spectrometry. We demonstrate that this analysis can be carried out either in cation exchange or in reversed-phase separation modes. The reversed-phase separation yields a better performance in terms of resolution compared with the cation exchange method. The measurement of commercial glyphosate herbicide samples show its principal applicability and reveals a wide range of δ¹³C values between ?24 and ?34 ‰ for different manufacturers. The absolute minimum amounts required to perform a precise and accurate determination of carbon isotope compositions of glyphosate and AMPA were in the sub-microgram range. The method proposed is sensitive enough to further perform the experiments that are necessary to better understand the carbon isotope fractionation associated to the natural degradation of glyphosate into AMPA. Furthermore, it can be used for contaminant source allocation and product authenticity as well.     

Use of multiply charged atomic ions for isotope ratio mass spectrometry

We have investigated the use of multiply charged atomic ions for the measurement of isotopic ratios of gaseous and vapour samples. We use a mass spectrometer system incorporating an electron cyclotron resonance (ECR) ion source for this purpose. In the cases of carbon, nitrogen and oxygen, the selection of the 2+ atomic species is found to be the most effective for obtaining reliable isotopic ratios. Using samples of carbon dioxide, nitrogen, air and water vapour, we have demonstrated the determination of the isotopic ratios 13C/12C, 15N/14N, 17 O/16 O and 18 O/16 O. For oxygen, this technique offers an alternative to the equilibration or purification methods normally required to obtain isotopic ratios of water or other oxygen-containing samples. In particular, 17 O/16 O can be measured directly without isobaric interference from OH+. With typical ionization efficiencies of greater than 10%, ECR ion sources have the potential to enable measurements on very small samples. In addition to those evaluated in the present work, there is scope for application of this method to other sample types, to a variety of sampling methods, and to other elements.     

Coupled Si and O isotope measurements of meteoritic material by laser fluorination isotope ratio mass spectrometry

We present a procedure for the determination of the isotopic ratios of silicon and oxygen from the same aliquot of anhydrous silicate material. The sample is placed in a bromine pentafluoride atmosphere as it is heated with a CO₂ laser system releasing silicon tetrafluoride and oxygen gasses. The oxygen gas is then purified to remove other reaction by‐products through several liquid nitrogen traps before being captured onto a molecular sieve and transferred to an isotope ratio mass spectrometer. The silicon tetrafluoride gas is then purified using a supplementary line by repeatedly freezing to ?196°C with liquid nitrogen and then thawing with an ethanol slurry at ?110°C through a series of metal and Pyrex traps. The purified gas is then condensed into a Pyrex sample tube before it is transferred to an isotope ratio mass spectrometer for silicon isotope ratio measurements. This system has silicon yields of greater than 90% for pure quartz, olivine, and garnet standards and has a reproducibility of ±0.1‰ (2σ) for pure quartz for both oxygen and silicon isotope measurements. Meteoritic samples were also successfully analyzed to demonstrate this system's ability to measure the isotopic ratio composition of bulk powders with precision. This unique technique allows for the fluorination of planetary material without the need for wet chemistry. Though designed to analyze small aliquots of meteoritic material (1.5 to 3 mg), this approach can also be used to investigate refractory terrestrial samples where traditional fluorination is not suitable.     

delta34S measurements on organic materials by continuous flow isotope ratio mass spectrometry

Sulfur (S) isotope ratios of thoroughly dried organic samples were measured by direct thermal decomposition in an elemental analyzer coupled to an isotope ratio mass spectrometer in continuous flow mode (EA-CF-IRMS). For organic samples of up to 13 mg weight and with total S contents of more than 10 microg, the reproducibility of the delta34S(organic) values was +/-0.4 per thousand or better. However, the delta34S values of organic samples measured directly by online EA-CF-IRMS analysis were between 0.3 and 2.9 per thousand higher than those determined on BaSO4 precipitates produced by Parr Bomb oxidation from the same sample material. Our results suggest that structural oxygen in organic samples influences the oxygen isotope ratios of the SO2 produced from organic samples. Consequently, SO2 generated from organic samples appears to have different 18O/16O ratios than SO2 generated from BaSO4 precipitates and inorganic reference materials, resulting in a deviation from the true delta34S values because of 32S16O18O contributions to mass 66. It was shown that both the amount of structural oxygen in the organic sample, and the difference of the oxygen isotope ratios between organic samples and tank O2, influenced the magnitude of the observed deviation from the true delta34S value after direct EA-CF-IRMS analysis of organic samples. Suggestions are made to correct the difference between measured delta34S(organic) and true delta34S values in order to obtain not only reproducible, but also accurate S isotope ratios for organic materials by EA-CF-IRMS.     

Determination of Cd and Zn by isotope dilution-thermal ionisation mass spectrometry using a sequential analysis procedure

Isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) was used to examine the certified Cd and Zn content of 4 Certified Reference Materials (CRMs); 2 soils: GBW07401 and GBW07405, 1 plant CRM060 and an animal tissue SRM1566a. The CRMs were chosen to be of contrasting origin and Cd:Zn content. Three digestion procedures were compared: (i) an open tube aqua regia procedure (ii) microwave digestion using Teflon bombs and (iii) hydrofluoric acid (HF) digestion using PTFE bombs. The Cd and Zn levels obtained using ID-TIMS all fell within the published certified range for the CRMs. This was the case regardless of the digestion procedure used, although HF digestion tended to yield marginally higher levels than the other procedures and in one instance, Cd in GBW07401, was significantly different (P<0.05) from the certified range. A filament loading procedure was developed, to allow sequential analysis of Cd and Zn on the same single filament during thermal ionisation mass spectrometry analysis. The sequential analysis technique was evaluated to ensure that Zn did not fractionate during Cd analysis and there was no inter-element interference. No marked difference in the precision and accuracy of the isotope ratio measurements were obtained from sequential element analyses on the same filament when compared to individual element analyses for a range of standard solutions or for sample digests. The most efficient procedure in terms of costs and productivity for future work of this kind would be a combination of microwave digestion and sequential analysis of Cd and Zn on the same filament.     

High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry

A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2 L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a ²⁰⁷Pb–²⁰⁴Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28 ± 21 pg (1sd) and typical Pb recoveries of 40–60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12 ± 4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700–1500 ppm and 1000–2000 ppm were achieved for ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor ²⁰⁴Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the ²⁰⁶Pb/²⁰⁴Pb ratios are well correlated with ²⁰⁷Pb/²⁰⁶Pb, underlining the significant improvement achieved in the measurement of the minor ²⁰⁴Pb isotope.     

Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements

In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic (¹³³Cs) whereas cesium in spent fuels has 4 isotopes (¹³³Cs, ¹³⁴Cs, ¹³⁵Cs, and ¹³⁷Cs). As no standard reference material is available to evaluate the accuracy of Cs isotopic measurements, a comparison of cesium isotopic composition in spent nuclear fuels has been performed between Thermal Ionization Mass Spectrometry (TIMS) and a new method involving Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) measurements. For TIMS measurements, isotopic fractionation has been evaluated by studying the behavior of cesium isotope ratios (¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs) during the analyses. For MC-ICPMS measurements, the mass bias effects have been corrected with an external mass bias correction using elements (Eu and Sb) close to cesium masses. The results obtained by the two techniques show good agreement: relative difference on ¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs ratios for two nuclear samples, analyzed after chemical separation, ranges from 0.2% to 0.5% depending on the choice of reference value for mass bias correction by MC-ICPMS. Finally the quantification of the ¹³⁵Cs/²³⁸U ratio by the isotope dilution technique is presented in the case of a MOx (mixed oxide) spent fuel sample. Evaluation of the global uncertainties shows that this ratio could be defined at an uncertainty of 0.5% (k = 2). The intercomparison between two independent mass spectrometric techniques is fundamental for the evaluation of uncertainty when no isotopic standard is available.     

Application of the total evaporation technique to chromium isotope ratio measurement by thermal ionization mass spectrometry

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.     

Polynomial mass bias functions for the internal standardization of isotope ratio measurements by multi-collector inductively coupled plasma mass spectrometry

The development and application of a calibration strategy for routine isotope ratio analysis by multi-collector inductively coupled plasma mass spectrometry (ICP-MS) is described and assessed. Internal standardization was used to account for the mass dependant determinate error (mass bias). The general solution for polynomial isotope ratio mass bias functions for use with internal standardization and isotope ratio measurements by multi-collector inductively coupled plasma mass spectrometry was derived. The resulting linear isotope ratio mass bias function was demonstrated to be mathematically consistent and experimentally realistic for the analysis of acidified aqueous solutions of analyte and internal standard elements (clean solutions) by multi-collector inductively coupled plasma mass spectrometry.     

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.