Comparative studies on the certification of reference materials by ICPMS and TIMS using isotope dilution procedures

A comparison of different isotope dilution mass spectrometric (IDMS) procedures using inductively coupled plasma mass spectrometry (ICPMS) and thermal ionization mass spectrometry (TIMS) was carried out to examine the degree of equivalence between the used procedures in terms of requirements for reference material certification. The comparison was based on the measurement results and their uncertainties. The sample used in this study is a pure zinc metal to be certified by the Bureau Communie de Référence (BCR) for amount contents of different trace elements. This study focuses on cadmium and thallium. The TIMS values contributed to the certified values. To guarantee identical conditions as far as possible for the procedures under investigation, the samples were split into subsamples after spiking and digestion took place. Thus, every IDMS procedure started with an identical set of samples. In total, four different IDMS procedures and one external calibration procedure using internal standardization as an example of routine analysis were applied. The IDMS procedures divide in a group with and a group without trace/matrix separation. Multicollector TIMS (TI-MC-MS) and multicollector ICPMS (ICP-MC-MS) were used in combination with trace/matrix separation, whereas quadrupole ICPMS (ICP-QMS) and ICP-MC-MS were also applied to nonseparated samples. All IDMS results agree well within their combined uncertainties, while some results from the external calibration procedure do not. IDMS results obtained by ICPMS without separation are comparable to those obtained by TI-MC-MS with separation regarding precision and accuracy. The smallest uncertainties were achieved using ICP-MC-MS in combination with trace/matrix separation.     

Isotope dilution mass spectrometry — A primary method of measurement and its role for RM certification

This article describes the application of isotope dilution mass spectrometry (IDMS) to the field of reference material (RM) characterisation focusing on the approach, which is applied by the IDMS group at BAM. Emphasis is placed on IDMS measurements of highest analytical quality. Basic principles as well as the equation system are being recalled. Different calibration strategies, such as single, double or triple IDMS, are critically reviewed and the achievable uncertainties are discussed. Differences in the application of thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICPMS) are discussed as well as differences between different types of mass spectrometers such as single collector versus multi-collector or quadrupole versus magnetic sector instruments. Possible sources of errors and bias are mentioned and correction models introduced and applied within the past years are discussed. Several examples for RM characterisations in the field of elemental analysis are shown, each demonstrating excellent analytical quality. In general it can be stated that IDMS is the most important reference method for elemental analysis, offering highest accuracy and precision or smallest measurement uncertainties, when properly applied. Thus IDMS represents by far the best suited reference method for RM characterisation. Due to its universal applicability IDMS offers sufficient potential to follow future needs in analytical chemistry as well as in the RM sector     

High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios ((44)Ca/(42)Ca and (44)Ca/(43)Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10?000; Ca/Ti > 10?000?000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ(44/42)Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).     

Evaluation of the Isotope Ratio Performance of an Axial Time-of-Flight ICP Mass Spectrometer

The isotope ratio performance of an axial time-of-flight ICP mass spectrometer (Renaissance TOF-ICPMS, LECO Corp.) was evaluated. The isotope ratio precision, expressed as the relative standard deviation (RSD) for 10 successive measurements, was evaluated using multielement standard solutions with analyte concentrations of 50-500 μg/L. The influence of the acquisition time per replicate measurement was studied by varying it between 0.5 and 300 s. For an acquisition time of 30 s per replicate and an elemental concentration of 500 μg/L, typical isotope ratio precisions of ≤0.05% RSD were obtained. The fact that this isotope ratio precision can be obtained for many ratios simultaneously is an especially attractive feature of TOF-ICPMS. In contrast to what was expected, increasing the acquisition time per replicate to values of >30 s resulted in a slightly deteriorated isotope ratio precision. At short acquisition times (<10 s), isotope ratio precisions similar to, or better than, the best values ever reported for quadrupole-based instruments were obtained. The latter observation remained valid when working with transient signals of corresponding duration. Mass discrimination was observed to be analogous to that observed with other types of ICPMS instrumentation (～1% per mass unit at midmass). The accuracy attainable was evaluated by comparing Pb isotopic results for a "natural" Pb standard solution obtained by TOF-ICPMS with those obtained by thermal ionization mass spectrometry.     

Chlorine isotope analysis of submicromole organochlorine samples by sealed tube combustion and thermal ionization mass spectrometry

Improved sensitivity in the analysis of stable chlorine isotopes of organochlorines (delta(37)Cl-OCl) has been established using sealed tube combustion in conjunction with thermal ionization mass spectrometry (TIMS). TIMS of chlorine isotopes was performed on <85 nmol of Cl with an achievable precision of <0.25 per thousand for pure inorganic chloride samples and 0.46 per thousand for chloride liberated from organochlorines (OCls). This makes possible significant reductions in the overall sample size requirement, as compared to the techniques of gas source stable isotope ratio mass spectrometry (SIRMS). Yields in excess of 99% were demonstrated in the dechlorination of <0.14 micromol 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), and the overall yield, including purification of liberated chloride, was 86-97%. The accuracy of TIMS in the measurement of chlorine isotopes derived from OCls was confirmed by analysis of a DDT sample previously analyzed with SIRMS.(9) Using the described method for TIMS, the DDT sample gave a bulk chlorine isotope ratio of delta(37)Cl -4.42 +/- 0.46 per thousand (1sigma). The reported value from SIRMS analysis is -4.34 +/- 0.25 per thousand, indicating the conformity of the two methods.     

Fe isotope variations in natural materials measured using high mass resolution multiple collector ICPMS

We present the first measurements of Fe isotope variations in chemically purified natural samples using high mass resolution multiple-collector inductively coupled plasma source mass spectrometry (MC-ICPMS). High mass resolution allows polyatomic interferences at Fe masses to be resolved (especially, (40)Ar(14)N(+), (40)Ar(16)O(+), and (40)Ar(16)OH(+)). Simultaneous detection of Fe isotope ion beams using multiple Faraday collectors facilitates high-precision isotope ratio measurements. Fe in basalt and paleosol samples was extracted and purified using a simple, single-stage anion chemistry procedure. A Cu "element spike" was used as an internal standard to correct for variations in mass bias. Using this procedure, we obtained data with an external precision of 0.03-0.11 per thousand and 0.04-0.15 per thousand for delta(56/54)Fe and delta(57/54)Fe, respectively (2sigma). Use of Cu was necessary for such reproducibility, presumably because of subtle effects of residual sample matrix on mass bias. These findings demonstrate the utility of high-resolution MC-ICPMS for high-precision Fe isotope analysis in geologic and other natural materials. They also highlight the importance of internal monitoring of mass bias, particularly when using routine methods for Fe extraction and purification.     

Simultaneous sample preparation and species-specific isotope dilution mass spectrometry analysis of monomethylmercury and tributyltin in a certified oyster tissue

A rapid, accurate, sensitive, and simple method for simultaneous speciation analysis of mercury and tin in biological samples has been developed. Integrated simultaneous sample preparation for tin and mercury species includes open focused microwave extraction and derivatization via ethylation. Capillary gas chromatography-inductively plasma mass spectrometry (CGC-ICPMS) conditions and parameters affecting the analytical performance were carefully optimized both for species-specific isotope dilution analysis of MMHg and TBT and for conventional analysis of MBT and DBT201Hg-enriched monomethylmercury and 117Sn-enriched tributyltin were used for species-specific isotope dilution mass spectrometry (SIDMS) analysis. As important, accurate isotope dilution analysis requires equilibration between the spike and the analyte to achieve successful analytical procedures. Since the spike stabilization and solubilization are the most critical and time-consuming steps in isotope dilution analysis, different spiking procedures were tested. Simultaneous microwave-assisted spike stabilization and solubilization can be achieved within less than 5 min. This study originally introduces a method for the simultaneous speciation and isotope dilution of mercury and tin in biological tissues. The sample throughput of the procedure was drastically reduced by fastening sample preparation and GC separation steps. The accuracy of the method was tested by both external calibration analysis and species-specific isotope dilution analysis using the first biological reference material certified for multielemental speciation (oyster tissue, CRM 710, IRMM). The results obtained demonstrate that isotope dilution analysis is a powerful method allowing the simultaneous speciation of TBT and MMHg with high precision and excellent accuracy. Analytical problems related to low recovery during sample preparation are thus minimized by SIDMS. In addition, a rapid procedure allows us to establish a performant routine method using CGC-ICPMS technique.     

Lithium isotope composition of basalt glass reference material

We present data on the lithium isotope compositions of glass reference materials from the United States Geological Survey (USGS) and the National Institute of Standards and Technology (NIST) determined by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), thermal ionization mass spectrometry (TIMS), and secondary ionization mass spectrometry (SIMS). Our data on the USGS basaltic glass standards agree within 2 per thousand, independent of the sample matrix or Li concentration. For SIMS analysis, we propose use of the USGS glasses GSD-1G (delta(7)Li 31.14 +/- 0.8 per thousand, 2sigma) and BCR-2G (delta(7)Li 4.08 +/- 1.0 per thousand, 2sigma) as suitable standards that cover a wide range of Li isotope compositions. Lithium isotope measurements on the silica-rich NIST 600 glass series by MC-ICPMS and TIMS agree within 0.8 per thousand, but SIMS analyses show systematic isotopic differences. Our results suggest that SIMS Li isotope analyses have a significant matrix bias in high-silica materials. Our data are intended to serve as a reference for both microanalytical and bulk analytical techniques and to improve comparisons between Li isotope data produced by different methodologies.     

Detection limit of isotope dilution mass spectrometry

The detection limit is an important figure of merit for evaluating instrumentation and analytical methods. While the detection limit for techniques using linear calibration functions has been studied extensively, this fundamental metric has rarely been discussed for mass spectrometry that bases the calibration on the principle of isotope dilution. We have developed a formulation for the detection limit for isotope dilution mass spectrometry (IDMS) after a thorough analysis of the uncertainty of IDMS measurements. The new formulation describes the IDMS detection limit as a function of the enrichment of the isotopic spike and the linear calibration detection limits measured at the masses for the isotope ratio measurement.     

Determination of radium isotope ratios and abundances in geologic samples by thermal ionization mass spectrometry

We describe chemical separation and mass spectrometric procedures for the measurement of radium isotopes in geologic samples. These methods provide 226Ra/228Ra ratio measurements for 1 g or less of rock sample containing subpicogram amounts of radium with precision better than 1.5% (95% confidence level). Radium-226 concentrations were measured by isotope dilution for smaller sample sizes (100-500 mg) containing as little as 1-10 fg of total 226Ra with similar high precision.     

Improvement of measurement precision of SPME-GC/MS determination of tributyltin using isotope dilution calibration

A unique approach was developed to improve the precision of quantification of tributyltin (TBT) in sedimentsby solid phase microextraction (SPME) using isotope dilution GC/MS. The precision of the analytical technique was initially evaluated using standard calibration solutions. In selective ion monitoring (SIM) mode, the relative standard deviation (RSD) obtained for TBT based on peak area response was 18% (n = 11). When an internal standard, tripropyltin (TPrT), was used, the RSD decreased to 12%. A significant improvement in the precision using SPME was noted when a 117Sn-enriched TBT spike was employed; the RSD decreased 4-fold to 3%. Detection limits of 0.2 and 20 ng(Sn) L(-1) were achieved with SPME sampling and liquid-liquid extraction, respectively. Six analyses were performed for determination of TBT in PACS-2 sediment Certified Reference Material using both standard additions and isotope dilution procedures. For the latter, a 117Sn-enriched TBT spike was used. A concentration of 0.88 +/- 0.03 microg g(-1) (RSD 3.4%) obtained using standard additions was in good agreement with the certified value of 0.98 +/- 0.13 microg g(-1) as tin. Concentrations found using isotope dilution were 0.895 +/- 0.015 microg g(-1) (RSD 1.73%) as tin and 0.874 +/- 0.014 microg g(-1) (RSD 1.66%) as tin using a liquid-liquid extraction and SPME sampling, respectively. A 2-fold improvement in the precision of TBT concentration measurement using isotope dilution was clearly achieved, demonstrating its superiority in providing more accurate and precise results as compared to the method of standard additions. The isotope dilution technique eliminated the problem of poor reproducibility, which typically plagues SPME.     

Determination of selenomethionine and selenocysteine in human serum using speciated isotope dilution-capillary HPLC-inductively coupled plasma collision cell mass spectrometry

A method for the accurate determination of selenoamino acids in human serum by HPLC-ICPMS was developed using the species-specific isotope dilution analysis principle. A serum sample was enzymatically digested with a mixture of lipase and protease after derivatization of the selenocysteine residues with iodoacetamide. The selenoamino acid fraction was isolated by size exclusion LC followed by the separation of selenomethionine and the carboxymethylated selenocysteine by capillary HPLC. The isotope-specific determination of 77Se and 80Se was achieved on-line by ICP collision cell MS allowing the removal of polyatomic interferences. Quantification was carried out by isotope dilution using a 77Se-labeled selenomethionine spike and the determination of the 77Se/80Se ratio in the cHPLC selenomethionine peak. The accurately determined selenomethionine was used as an internal standard for the selenocysteine determination from the same chromatogram. The modification of the previously developed cHPLC-ICPMS interface allowed the reduction of the absolute detection limits twice (down to the 75-fg level), which resulted in the lowest ever reported procedural detection limits (below 0.5 ng g(-1) for a 450-mg serum sample). The precision was less than 5% RSD. The method was validated by the mass balance of selenium (amino acid incorporated vs total).     

Sources of uncertainty in isotope ratio measurements by inductively coupled plasma mass spectrometry

A model is presented describing the effects of dead time and mass bias correction factor uncertainties, flicker noise, and counting statistics on isotope ratio measurement precision using inductively coupled plasma mass spectrometry (ICPMS) with a single collector. Noise spectral analysis is exploited to enable estimation of the flicker noise parameters. For the instrument used, the flicker noise component exhibited a fairly weak frequency (t) dependence (is proportional to f -0.33+/-0.12), but was directly proportional to the total number of counts, Q. As white noise, determined by counting statistics, is given by Q0.5, the isotope ratio measurement uncertainties will actually cease to improve when Q exceeds a certain threshold. This would suggest that flicker noise could become the limiting factor for the precision with which isotope ratios can be determined by ICPMS. However, under most experimental conditions, uncertainties associated with mass discrimination and dead time correction factors are decisive. For ratios up to approximately 22 (115In/113In), optimum major isotope count rates are generally below 0.3 MHz, for which precision in the mass discrimination factor is limiting. The model derived could be used as a starting point for determining optimum conditions and understanding the limitations of single-collector ICPMS for precise isotope ratio measurements.     

Use of Thermal Ionization Mass Spectrometry for Measuring the Oxygen Isotope Ratio in Uranium Oxides1,2

A method was developed for precise determination of oxygen isotope ratios in uranium oxides. Thermal ionisation mass spectrometry (TIMS) was used for direct measurements of n(U^{1 8}O⁺)/n(U^{1 6}O⁺) using the molecular species UO⁺. Suitable sample handling and filament preparation techniques were developed in order to obtain reproducible results and avoid oxygen contamination. The actual measurements were performed using the total evaporation method. By this technique the achieved precision for n(U^{1 8}O⁺)/n(U^{1 6}O⁺) measurements was in the range of 0.04%. The peak jump techniques was also used for measurements, and the results of both techniques are discussed. The TIMS measurement are verified by comparative measurements using secondary ion mass spectrometry (SIMS).     

Measurement of isotopes of light rare earth elements in the form of oxide ions: a new development in thermal ionization mass spectrometry

An isobaric interference free thermal ionization mass spectrometry (TIMS) method is presented here for the precise isotope measurements of light rare earth elements (LREEs). LREE isotopes can be measured in the form of monoxide ion (MO+), but the previous determinations of LREE isotopes in the form of oxide were hindered, notably by the 17O and 18O related isobaric interferences. In the present study, 16O-enriched oxygen was introduced into the ion source chamber via a specially designed gas inlet system. It was observed that the isobaric interferences caused by 17O and 18O were remarkably reduced by up to 6 and 70 times, respectively, compared to those caused by natural oxygen bleeding. Isotopic ratios of La, Ce, and Nd obtained without isobaric interference corrections show the excellent precision and accuracy in the present study. The results also shed some light on the formation mechanism of the measured oxide species in TIMS. Furthermore it promises more precise determination of LREE abundances and La-Ce and Sm-Nd ages in geochemistry and cosmochemistry.     

Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry

The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.     

Wood cellulose preparation methods and mass spectrometric analyses of delta13C, delta18O, and nonexchangeable delta2H values in cellulose, sugar, and starch: an interlaboratory comparison

Interlaboratory comparisons involving nine European stable isotope laboratories have shown that the routine methods of cellulose preparation resulted in data that generally agreed within the precision of the isotope ratio mass spectrometry (IRMS) method used: +/-0.2 per thousand for carbon and +/-0.3 per thousand for oxygen. For carbon, the results suggest that holocellulose is enriched up to 0.39 per thousand in 13C relative to the purified alpha-cellulose. The comparisons of IRMS measurements of carbon on cellulose, sugars, and starches showed low deviations from -0.23 to +0.23 per thousand between laboratories. For oxygen, IRMS measurements varied between means from -0.39 to 0.58 per thousand, -0.89 to 0.42 per thousand, and -1.30 to 1.16 per thousand for celluloses, sugars, and starches, respectively. This can be explained by different effects arising from the use of low- or high-temperature pyrolysis and by the variation between laboratories in the procedures used for drying and storage of samples. The results of analyses of nonexchangeable hydrogen are very similar in means with standard deviations between individual methods from +/-2.7 to +/-4.9 per thousand. The use of a one-point calibration (IAEA-CH7) gave significant positive offsets in delta2H values up to 6 per thousand. Detailed analysis of the results allows us to make the following recommendations in order to increase quality and compatibility of the common data bank: (1) removal of a pretreatment with organic solvents, (2) a purification step with 17% sodium hydroxide solution during cellulose preparation procedure, (3) measurements of oxygen isotopes under an argon hood, (4) use of calibration standard materials, which are of similar nature to that of the measured samples, and (5) using a two-point calibration method for reliable result calculation.     

Isotopic analysis of uranium in tree bark by ICP mass spectrometry: a strategy for assessment of airborne contamination

Isotopic analysis of uranium in tree bark by ICP mass spectrometry is proposed as a new measurement strategy for monitoring airborne contamination and for discrimination of nuclear and nonnuclear emission sources. A quadrupole-based ICP mass spectrometer equipped with a microconcentric nebulizer and membrane desolvator was used to provide high-sensitivity measurement. The limit of detection for uranium (238U) was 0.004 ng L(-1). Measurement precision (235U/238U) was between 0.2 and 0.5% RSD for isotopic SRMs (U005 and U015; concentration, 1 microg L(-1)) and ranged from 0.4 to 3.1% RSD for tree bark extracts (U concentration, 0.03-0.08 microg L(-1)). Bark samples collected from the Peak District National Park in Derbyshire (U.K.) exhibited a natural 235U/238U isotope ratio value (0.0072) whereas samples from Sellafield, West Cumbria (U.K.) showed depletion in 235U (235U/238U = 0.0053-0.0064).     

Understanding the enhanced ductility of Mg-Gd with Ca and Zn microalloying by slip trace analysis

This research studied the mechanisms of Ca and Zn microalloying on the enhancement of ductility of extruded Mg-Gd sheet by combing electron backscattered diffraction and slip trace analysis.The ductil-ity and microstructure of extruded Mg-0,6Gd and Mg-0.6Gd-0.3Ca-0,2Zn (wt％) sheets were investigated.Basal slip was the main deformation mode under investigation.Ca and Zn microalloying increased the frequency of grain boundaries (GBs) with misorientation angles (θs) ＜ 35°,promoted slip transfer across GBs and restricted the basal slip localization.In addition,there were a higher number of GB cracks homo-geneously distributed in the Mg-0.6Gd sheet than in the Mg-0.6Gd-0.3Ca-0.2Zn sheet,attributed to the increased cohesion of GBs.The enhancement of basal slip,the suppression of slip localization and the suppression of GB cracking were contributed to the increased ductility for Mg-0.6Gd-0.3Ca-0.2Zn sheet.     

Development of isotope dilution cold vapor inductively coupled plasma mass spectrometry and its application to the certification of mercury in NIST standard reference materials

An isotope dilution cold vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) method featuring gaseous introduction of mercury via tin chloride reduction has been developed and applied to the quantification and certification of mercury in various NIST standard reference materials: SRM 966 Toxic Metals in Bovine Blood (30 ng x mL(-1)); SRM 1641d Mercury in Water (1.6 microg x mL(-1)); and SRM 1946 Lake Superior Fish Tissue (436 ng x g(-1)). Complementary mercury data were generated for SRMs and NIST quality control standards using cold vapor atomic absorption spectroscopy (CVAAS). Certification results for the determination of mercury in SRM 1641d using two independent methods (ID-CV-ICPMS and CVAAS) showed a degree of agreement of 0.3% between the methods. Gaseous introduction of mercury into the ICPMS resulted in a single isotope sensitivity of 2 x 10(6) counts x s(-1)/ng x g(-1) for 201Hg and significantly reduced the memory and washout effects traditionally encountered in solution nebulization ICPMS. Figures of merit for isotope ratio accuracy and precision were evaluated at dwell times of 10, 20, 40, 80, and 160 ms using SRM 3133 Mercury Spectrometric Solution. The optimum dwell time of 80 ms yielded a measured 201Hg/202Hg isotope ratio within 0.13% of the theoretical natural value and a measurement precision of 0.34%, on the basis of three replicate injections of SRM 3133.