Accurate Determination of Isotope Ratios

Special instruments (isotope ratio mass spectrometers) are used to determine isotope ratios, when needed, to better than about 3%. Such special instruments are described in Chapters 6, 7, and 48. The methods of ionization and analysis for such precise measurements are not described here. 

The isotope patterns for two simple organometallic compounds in the molecular ion region (a) dimethylmercury and (b) dimethylplatinum. The seven isotopes of mercury show clearly and appear quite different from the six isotopes of platinum. Since there are only two carbon atoms, the contribution from C is negligible. 

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In order to reduce possible contamination problems during sample preparation, LA-ICP-MS is applied for the precise and accurate determination of isotope ratios at the trace and... 

S. Gas source mass spectrometry (GSMS) with electron impact (El) ion source produces nearly mono-energetic ions (similar to TIMS) and is an excellent tool for the high precision isotope analysis of light elements such as H, C, N and O, but also for S or Si.7,100,101 Precise and accurate measurements of isotope ratios have been carried out by gas source mass spectrometers with multiple ion collectors by a sample/standard comparison and the 8 values of isotope ratios were determined (see Equation 8.4). Electron impact ionization combined with mass spectrometry has been applied for elements which readily form gaseous compounds (e.g., C02 or S02) for the isotope analysis of carbon and sulfur, respectively). 

Van den Boom et al.150 have reported on the determination of silicon isotope ratio measurements in silicate materials by MC-ICP-MS (at a mass resolution of 2500 to resolve isobaric interferences) after sodium hydroxide sample digestion and purification of silicon. 829Si and 830Si have been determined for several silicon isotope standard reference materials. A precision for 830Si of 0.18-0.41 %o was achieved. Precise and accurate measurements of isotope ratios on transient signals by HPLC-MC-ICP-MS for nuclear application was performed by Giinther-Leopold et al.151... 

Yang, L. (2009) Accurate and precise determination of isotopic ratios by MC-ICP-MS a review. Mass Spectrom. Rev, 28, 990-1011. 

Doucet et described the determination of isotope ratios using LIBS in air at atmospheric pressure for partially resolved uranium-235-uranium-238 and hydrogen-deuterium isotope shift lines. A PLSl regression model could accurately predict the isotopic ratio under conditions where the application of traditional univariate approaches for hydrogen and uranium would not be achievable. 

For recognition of polyatomic interferences, monitoring several isotopes of one element is advised, as the natural isotope ratio is altered when interferences effect one of the isotopes. The precise determination of isotope ratios depends on an accurate determination of detector dead time and mass-bias correction [29]. Unsatisfactory sensitivity is still a problem in samples with very low species concentration, for example, in body fluids from persons witiaout elevated exposure to trace metals. In this case, the most abundant isotope of the element should be monitored unless it is significantly interfered with. In addition, a high-efficiency nebulizer could be used for improved sample introduction into the ICP-MS. 

Authenticity evaluation has recently received increased attention in a number of industries. The complex mixtures involved often require very high resolution analyses and, in the case of determining the authenticity of natural products, very accurate determination of enantiomeric purity. Juchelka et al. have described a method for the authenticity determination of natural products which uses a combination of enantioselective multidimensional gas chromatography with isotope ratio mass spectrometry (28). In isotope ratio mass spectrometry, combustion analysis is combined with mass spectrometry, and the ratio of the analyte is measured versus a... 

In isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) the spike, the unspiked and a spiked sample are measured by ICP-MS in order to determine the isotope ratio. Using this technique, more precise and accurate results can be obtained than by using a calibration graph or by standard addition. This is due to elimination of various systematic errors. Isotopes behave identically in most chemical and physical processes. Signal suppression and enhancement due to the matrix in ICP-MS affects both isotopes equally. The same holds for most long-term instrumental fluctuations and drift. Accuracy and precision obtained with ID-ICP-QMS are better than with other ICP-QMS calibration... 

Secondary isotope effects are small. In fact, most of the secondary deuterium KIEs that have been reported are less than 20% and many of them are only a few per cent. In spite of the small size, the same techniques that are used for other kinetic measurements are usually satisfactory for measuring these KIEs. Both competitive methods where both isotopic compounds are present in the same reaction mixture (Westaway and Ali, 1979) and absolute rate measurements, i.e. the separate determination of the rate constant for the single isotopic species (Fang and Westaway, 1991), are employed (Parkin, 1991). Most competitive methods (Melander and Saunders, 1980e) utilize isotope ratio measurements based on mass spectrometry (Shine et al., 1984) or radioactivity measurements by liquid scintillation (Ando et al., 1984 Axelsson et al., 1991). However, some special methods, which are particularly useful for the accurate determination of secondary KIEs, have been developed. These newer methods, which are based on polarimetry, nmr spectroscopy, chromatographic isotopic separation and liquid scintillation, respectively, are described in this section. The accurate measurement of small heavy-atom KIEs is discussed in a recent review by Paneth (1992). 

The masses of isotopes can be measured with accuracies better than parts per billion (ppb), e.g., m40Ar = 39.9623831235 0.000000005 u. Unfortunately, determinations of abundance ratios are less accurate, causing errors of several parts per million (ppm) in relative atomic mass. The real limiting factor, however, comes from the variation of isotopic abundances from natural samples, e.g., in case of lead which is the final product of radioactive decay of uranium, the atomic weight varies by 500 ppm depending on the Pb/U ratios in the lead ore. [8]... 

The reverse isotope dilution technique can be applied for accurate determination of the Mg contents in a sample, sample, on applying equation 7, by measuring the isotope ratio of a selected pair of stable isotopes, in a weighed mixmre of the sample with an isotopically enriched CRM. The average atomic masses m and the isotopic ratios R of Mg in the enriched CRM and in nature are known. The method was applied for determination of Mg in plant material using a CRM isotopically enriched with Mg, measuring with an ICP/MS instruments. ... 

Geochronology for age dating of minerals is a major field in earth sciences, includes measurements of isotope ratios and requires advanced sensitive, precise and accurate mass spectrometric techniques. The determination of the age of the Earth has been of significant interest for hundreds... 

Isotope Ratio Measurements The analysis of milk samples for the accurate determination of its constituent elements has also been done by isotope dilution analysis [34, 102, 103]. For that purpose, an enriched isotope of the element or elements to be determined is spiked to the sample, altering the natural isotopic composition of the element to be analyzed. By measuring the altered... 

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