Determination of lithium isotopic composition by thermal ionization mass spectrometry in seawater

The isotopic composition of lithium in seawater has been determined by thermal ionization mass spectrometry (TIMS) based on the use of lithium hydroxide as the ion source. Isotopic measurements in a reference material supplied by IAEA (L-SVEC Li₂CO₃) were made to check the reproducibility of the method and ⁶Li indicates mobilization of light isotope of lithium form the sediment.     

Absolute isotopic composition and atomic weight of neodymium using thermal ionization mass spectrometry

Synthetic mixtures prepared gravimetrically from highly enriched isotopes of neodymium in the form of oxides of well-defined purity were used to calibrate a thermal ionization mass spectrometer. A new error analysis was applied to calculate the final uncertainty of the atomic weight value. Measurements on natural neodymium samples yielded an absolute isotopic composition of 27.153(19) atomic percent (at.%) 142Nd, 12.173(18) at.% 143Nd, 23.798(12) at.% 144Nd, 8.293(7) at.% 145Nd, 17.189(17) at.% 146Nd, 5.756(8) at.% 148Nd, and 5.638(9) at.% 150Nd, and the atomic weight of neodymium as 144.2415(13), with uncertainties given on the basis of 95% confidence limits. No isotopic fractionation was found in terrestrial neodymium materials.     

Precise determination of lithium isotopic composition by thermal ionization mass spectrometry in natural samples such as seawater

The isotopic composition of lithium in an NIST SRM 924 Li₂CO₃, isotopically enriched supplied by ORNL and in seawater has been determined by using thermal ionization mass spectrometry (TIMS) based on the use of lithium phosphate as the ion source. In order to minimize isotopic fractionation, the ion ratio was measured by using a triple filament technique. The method produces a stable, high intensity Li⁺ ion beam that allows measurement of ng quantities of lithium for several hours. Lithium was separated from sample matrix and further converted to LiOH by employing a two-column ion exchange process. The mass ratio of LiOH to phosphoric acid was nearly stoichiometric in relation to Li₃PO₄. Lithium isotopes in a reference material supplied by NIST (L-SVEC Li₂CO₃) was measured to check the reproducibility of the method. A comparison was made between two TIMS units equipped with different types of detectors (a Faraday cup and a secondary electron multiplier). This highly sensitive technique can be applied to determine isotopic composition of Li in enriched isotopes as well as in the examination of low concentration Li reservoirs.     

Simultaneous analysis of uranium and plutonium using thermal ionization mass spectrometry

Simultaneous isotopic analysis of uranium and plutonium using thermal ionization mass spectrometer coupled to a multi-collector detection assembly with 9 Faraday cups has been reported earlier. Subsequently investigations have been carried out (1) to understand the applicability of correction methodologies available to account for the contribution of²³⁸Pu at²³⁸U and (2) to evaluate the effectiveness of these methodologies on the accuracy of²³⁵U/²³⁸U atom ratio being determined, particularly when samples containing different U/Pu atom ratios. Isotopic fractionation for both U and Pu in the simultaneous isotopic analysis has been compared with the results of the individual analysis of these elements. The different isotopic fractionation factors observed for U were attributed to different conditions of analysis. There was no significant difference in the isotopic fractionation patterns for Pu. The consideration to extend this method to actual samples from our observations on synthetic samples with diferent U/Pu atom ratios containing U and Pu isotopic reference standards is described.     

Practical application of thermal ionization mass spectrometry for the determination of plutonium for the LANL Bioassay Program (LA-UR-00-1697)

Utilization of thermal ionization mass spectrometry as a routine analytical service provided to the Los Alamos National Laboratory Bioassay Program has evolved significantly since its implementation just over three years ago. Converting this unique research tool designed to support nuclear weapons testing to a quasi-production mode for the routine analysis of ~300 urine samples/year for ultra-low levels of plutonium has required resolution of numerous practical issues. These issues include clean-room sample preparation, adequate tracer recovery, customer specified turn-around times, throughput, water and urine blank values, statistical data reduction, and quality control and performance evaluation sample requirements.     

The measurement of the isotopic composition of plutonium in an Irish Sea sediment by mass spectrometry

Samples from sediment cores, collected from a site close to the Sellafield outfall and dated using conventional - and -spectrometry, have been analysed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Thermal Ionisation Mass Spectrometry (TIMS). This has provided information on the isotopic composition of plutonium in the liquid discharges from Sellafield; such information is not available using conventional -spectrometry alone. There was very good agreement between the²⁴⁰Pu/²³⁹Pu ratios obtained by the two MS methods. More recent discharges have been characterised by a progressive decrease in the relative proportion of²³⁹Pu.     

Experimental evaluation of239Pu,238Pu and233U spikes for determining plutonium concentration by thermal ionization mass spectrometry and alpha-spectrometry

Experimental evaluation on the use of²³⁹Pu spike in Isotope Dilution-Thermal Ionization Mass Spectrometry (ID-TIMS),²³⁸Pu spike in Isotope Dilution Alpha Spectrometry (IDAS) and²³³U as a Non-Isotopic Diluent in Alpha Spectrometry (N-IDAS), for determing plutonium concentration in samples with burn-up values in the range of 1,000–10,000 MWD/TU is done. Precision is determined by analyzing replicate aliquots from different samples using each of the three spikes. Accuracy is established by comparing the results with those obtained by using well recognized spike²⁴²Pu in ID-TIMS. It is shown that the use of²³⁹Pu spike with the latest generation thermal ionization mass spectrometers gives the best precision (0.2%), whereas the precision values of 0.5 and 1% can be obtained by using²³⁸Pu and²³³U spikes, respectively, on a routine basis. Reasons for the difference in the precision values are discussed, along with the merits and drawbacks on the use of different spike isotopes.     

Characterization of an improved thermal ionization cavity source for mass spectrometry

A new thermal ionization source for use with a quadrupole mass spectrometer has been designed and characterized. The new source provides significant advantages over the previously reported prototype source and traditional filament-type thermal ionization sources. The operational interface between the source and the quadrupole mass spectrometer has been redesigned. A vacuum interlock, a translational stage, and an adjustable insertion probe are added to improve the source performance. With these modifications, the source is easier to operate while maximizing sample throughput. In this work, the performance of the newly developed source is examined. The ionization efficiencies are measured with a quadrupole mass spectrometer. The efficiency values obtained with this system are comparable to those obtained from a large scale isotope separator. The relationships among the ionization potential, vapor pressure, and measured ionization efficiency results are discussed. The crucible lifetime has been quantitatively estimated by measuring the crucible sputtering rate. Diagnostic studies of the new source show that the crucible position is a crucial parameter for sensitivity and performance. Stability tests demonstrate that the source can be run several weeks at a fixed emission current without significant degradation.     

High-performance liquid chromatography-electronspray ionization mass spectrometry for determination of tiopronin in human plasma

A simple and sensitive HPLC/ESI-MS method for the determination of tiopronin in human plasma was described. Vitamin C and 2-mercaptoethanol (2-Me) were used as the reducer and the stabilitizer to release and stabilify tiopronin from a dimmer and mix forms with endogenous thiols in the treatment of plasma samples. The analytes were separated on a Johnson Spherigel analytical column packed with 5 microm C8 silica, using the formic acid aqueous solution (pH 4.5) including tris(hydroxymethyl) aminomethane (Tris) and 2-Me (0.5 and 1 mM, respectively) as a mobile phase. Cyclamate was used as the internal standard (I.S.) for the quantification of tiopronin. The correlation coefficient of the calibration curve were better than 0.998 in the range of 0.107-5.35 microg/ml in human plasma. The limit of quantification (LOQ) was 0.107 microg/ml (S/N 10:1, RSD 7.1%). The inter-day and intra-day accuracy was below 7.1 and 6.8%, respectively. As a preliminary application, this method has been successfully applied to the determination of tiopronin in the human plasma.     

A mobile mass spectrometry laboratory for isotopic ratio measurements of uranium and plutonium

A modified quadrupole mass spectrometer is housed in a van that serves as a mobile laboratory to provide on-site determinations of isotopic ratios and concentrations of uranium and plutonium. Each element can be determined at 1–3 ng levels with precisions of 1–2%.     

Rapid and precise determination of Sr and Nd isotopic ratios in geological samples from the same filament loading by thermal ionization mass spectrometry employing a single-step separation scheme

Thermal ionization mass spectrometry (TIMS) offers the excellent precision and accuracy of the Sr and Nd isotopic ratio analysis for geological samples, but this method is labour intensive, expensive and time-consuming. In this study, a new analytical protocol by TIMS is presented that aims at improving analytical efficiency and cutting down experimental cost. Using the single-step cation exchange resin technique, mixed Sr and rare earth elements (REEs) fractions were separated from matrix and evaporated to dryness. Afterwards, mixed Sr + REEs fractions were dissolved and loaded onto the same Re filament using 1 μL of 2 M HCl. Then, Sr and Nd were sequentially measured without venting using TIMS. In contrast to conventional TIMS methods, the merits of this analytical protocol are its cost- and time-saving adaptations. The applicability of our method is evaluated by replicated measurements of ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd for nine international silicate rock reference materials, spanning a wide range of bulk compositions. The typical internal precision in this study is ca. 0.001% (RSE) for ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd; the analytical results obtained for these standard rocks show a good agreement with reported values, indicating the effectiveness of the proposed method.     

Ion-pair liquid chromatography--atmospheric pressure ionization mass spectrometry for the determination of quaternary ammonium herbicides

High-performance liquid chromatography coupled with atmospheric pressure ionization mass spectrometry (electrospray and atmospheric pressure chemical ionization) has been used to characterize some quaternary ammonium herbicides (quats). The separation of these compounds was carried out using ion-pair chromatography with heptafluorobutyric acid (15 mM, pH 3.3) and acetonitrile gradient elution for successful coupling to mass spectrometry. Detection limits down to 0.1-4 micrograms l-1 were obtained for spiked tap water following a preconcentration step. Good reproducibilities (day-to-day and run-to-run) were also obtained.     

Atmospheric-pressure laser ionization: a novel ionization method for liquid chromatography/mass spectrometry

We report on the development of a new laser-ionization (LI) source operating at atmospheric pressure (AP) for liquid chromatography/mass spectrometry (LC/MS) applications. APLI is introduced as a powerful addition to existing AP ionization techniques, in particular atmospheric-pressure chemical ionization (APCI), electrospray ionization (ESI), and atmospheric pressure photoionization (APPI). Replacing the one-step VUV approach in APPI with step-wise two-photon ionization strongly enhances the selectivity of the ionization process. Furthermore, the photon flux during an ionization event is drastically increased over that of APPI, leading to very low detection limits. In addition, the APLI mechanism generally operates primarily directly on the analyte. This allows for very efficient ionization even of non-polar compounds such as polycyclic aromatic hydrocarbons (PAHs). The APLI source was characterized with a MicroMass Q-Tof Ultima II analyzer. Both the effluent of an HPLC column containing a number of PAHs (benzo[a]pyrene, fluoranthene, anthracene, fluorene) and samples from direct syringe injection were analyzed with respect to selectivity and sensitivity of the overall system. The liquid phase was vaporized by a conventional APCI inlet (AP probe) with the corona needle removed. Ionization was performed through selective resonance-enhanced multi-photon ionization schemes using a high-repetition-rate fixed-frequency excimer laser operating at 248 nm. Detection limits well within the low-fmol regime are readily obtained for various aromatic hydrocarbons that exhibit long-lived electronic states at the energy level of the first photon. Only molecular ions are generated at the low laser fluxes employed ( approximately 1 MW/cm(2)). The design and performance of the laser-ionization source are presented along with results of the analysis of aromatic hydrocarbons.     

Determination of rubidium by isotope dilution—inductively-coupled plasma mass spectrometry as an alternative to thermal ionization mass spectrometry

The combined techniques of inductively coupled plasma mass spectrometry (ICP-MS) and isotope dilution yield as much as a three-fold improvement in precision for trace-level rubidium determinations in geological materials over conventional isotope dilution using thermal ionization mass spectrometry (TIMS). Rubidium determinations by TIMS, precise to 0.6% (1 s.d.), are hindered by uncorrectable fractionation effects, whereas fractionation can be monitored during ICP-MS determinations, providing results as precise as 0.17% (1 s.d.). Precise rubidium data are critical for high-precision RbSr geochronology.     

Quantitative determination of DNA adducts using liquid chromatography/electrospray ionization mass spectrometry and liquid chromatography/high-resolution inductively coupled plasma mass spectrometry

The quantitative determination of nucleotides from DNA modified by styrene oxide is described using a combination of inductively coupled plasma high-resolution mass spectrometry (ICP-HRMS) and electrospray ionization mass spectrometry (ESI-MS), both interfaced to reversed-phase high-performance liquid chromatography (HPLC). LC/ICP-MS (resolution > 1500 to discriminate against 15N16O+ and 14N16OH+) was employed to determine quantitatively the content of modified nucleotides in standard solutions based on the signal of phosphorus; phosphoric acid served as an internal standard. By means of the standard addition technique the sensitivity of the LC/ESI-MS approach was subsequently determined. Since a comparison of UV, ICP and ESI-MS data suggested that in ESI-MS the ionization efficiency of the adducts is identical within the error limits, quantitative determination of all adducts is possible. For LC/ESI-MS with single ion monitoring, the detection limit for styrene oxide adducts of nucleotides was determined to be 20 pg absolute or 14 modified in 10(8) unmodified nucleotides in a 5 micrograms DNA sample, which comes close to the best methods available for the detection of chemical modifications in DNA.     

Acetate, propionate and butyrate in plasma: determination of the concentration and isotopic enrichment by gas chromatography/mass spectrometry with positive chemical ionization

This study describes a rapid and simple method to determine short-chain fatty acid (SCFA) concentrations and their isotopic enrichments (M(0) + 1 and M(0) + 2) in human plasma. Sample preparation involves SCFA extraction and derivatization with 1-(tert-butyldimethylsilyl)imidazole. Gas chromatography/mass spectrometry was performed using chemical ionization with ammonia as the reagent gas. Outstanding resolution, excellent linearity and good detection limits were obtained. Inter-assay and intra-assay repeatability was below 10% and 3% respectively for SCFA concentration. Inter-assay repeatability was below 5%, 4%, 6%, and 14% for isotopic enrichment determination of [1-(13)C]acetate and [1,2-(13)C(2)]acetate, [1-(13)C]propionate and [1-(13)C]butyrate respectively, with intra-assay being below 6%. Such SCFA concentrations and isotopic enrichments were determined in the plasma of rats infused with a (13)C-labeled SCFA. The turnovers of acetate, propionate and butyrate in rats were 19 micromol kg(-1) min(-1), 2.6 micromol kg(-1) min(-1), 0.3 micromol kg(-1) min(-1) respectively.     

Electrospray ionization mass spectrometry of 5-methyl-2'-deoxycytidine and its determination in urine by liquid chromatography/electrospray ionization tandem mass spectrometry.

The behaviour of 5-methyl-2'-deoxycytidine (m(5)dCyd, claimed to be a potential marker for leukaemia) during the electrospray process was studied. In particular, considerations concerning the effect of solution chemistry (e.g. analyte concentration, pH, etc.) on electrospray ionization mass spectra were drawn. Furthermore, a procedure using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) for the determination of urinary m(5)dCyd is described. The method is simple, sensitive and highly specific. The pre-treatment procedure gave an average recovery of 79% (relative standard deviation (RSD) of 3%). Method performance was evaluated on spiked urine samples covering the concentration range from 50 ng/mL to 10 microgram/mL, the same as that of an existing inhibition ELISA method. Contrary to findings based on this immunoassay technique, urinary m(5)dCyd in healthy individuals was not detectable and did not increase in the presence of the malignant disease.     

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.     

A multiple ion counter total evaporation (MICTE) method for precise analysis of plutonium by thermal ionization mass spectrometry

Journal of Radioanalytical and Nuclear Chemistry - This paper presents a total evaporation method for the analysis of sub-picogram quantities of Pu, utilizing an array of multiple ion counters....