Mass spectrometry isotopic abundance ratios

Quantities of plutonium-241, a beta-particle emitter, can be quantified from (1) assumed isotopic abundance ratios, (2) estimated in-growth of its progeny americion-241 by gamma spectrometry, or by (3) mass spectrometry (Bernhardt 1976). Americium-241 is produced from the beta decay of plutonium-241 and, therefore, can be used to indirectly measure the concentration of plutonium-241 (Metz and Waterbury 1962). Direct determination of plutonium-241 by measurement of its low energy beta-particle decay has been reported using liquid scintillation analysis (Martin 1986). 

Demmelmair, H., Schmidt, H.L. (1993) Precise 513C determination in the range of natural abundance on amino acids from protein hydrolysates by gas chromatography-isotope ratio mass spectrometry. Isotopes in Environmental and Health Studies, 29, 237-250. 

Baxter, D.C., Rodushkin, 1., Engstrom, E., and Malinovsky, D. (2006) Revised exponential model for mass bias correction using an internal standard for isotope abundance ratio measurements by multi-collector inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom., 21, 427-430. 

Singleton K E, Cooks R G, Wood K V 1983 Utilization of natural isotopic abundance ratios in tandem mass spectrometry. Anal Chem 55 762-764... 

The previous discussion has centered on how to obtain as much molecular mass and chemical structure information as possible from a given sample. However, there are many uses of mass spectrometry where precise isotope ratios are needed and total molecular mass information is unimportant. For accurate measurement of isotope ratio, the sample can be vaporized and then directed into a plasma torch. The sample can be a gas or a solution that is vaporized to form an aerosol, or it can be a solid that is vaporized to an aerosol by laser ablation. Whatever method is used to vaporize the sample, it is then swept into the flame of a plasma torch. Operating at temperatures of about 5000 K and containing large numbers of gas ions and electrons, the plasma completely fragments all substances into ionized atoms within a few milliseconds. The ionized atoms are then passed into a mass analyzer for measurement of their atomic mass and abundance of isotopes. Even intractable substances such as glass, ceramics, rock, and bone can be examined directly by this technique. 

This accurate measurement of the ratio of abundances of isotopes is used for geological dating, estimation of the ages of antiquities, testing athletes for the use of banned steroids, examining fine details of chemical reaction pathways, and so on. These uses are discussed in this book under various headings concerned with isotope ratio mass spectrometry (see Chapters 7, 14, 15, 16, 17, 47, and 48). 

Routine mass spectrometry can be used to identify many elements from their approximate ratios of isotope abundances. For example, mercury-containing compounds give ions having the seven isotopes in an approximate ratio of 0.2 10.1 17.0 23.1 13.2 29.7 6.8. 

For marble provenance studies, the most successful technique seems to be the measurement, through mass spectrometry, of the abundance ratios of the stable isotopes of carbon and oxygen (116). However, no single technique appears to provide unequivocal results, especially in cases such as the different Mediterranean sources, and a combination is often necessary to arrive at an approximate place of origin (117). 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

In recent years, together with enantioselective analysis, the determination of the natural abundance of stable isotopes by means of stable isotope ratio mass spectrometry (TRMS) can be very useful for the assignment of the origin of foods and food ingredients, and of authenticity evaluation (24). 

Different isotopes differ in their atomic masses. The intensities of the signals from different isotopic ions allow isotopic abundances to be determined with high accuracy. Mass spectrometry reveals that the isotopic abundances in elemental samples from different sources have slightly different values. Isotopic ratios vary because isotopes with different masses have slightly different properties for example, they move at slightly different speeds. These differences have tiny effects at the level of parts per ten thousand (0.0001). The effects are too small to appear as variations In the elemental molar masses. Nevertheless, high-precision mass spectrometry can measure relative abundances of isotopes to around 1 part in 100,000. 

Volpe AM, Olivares JA, Murrell MT (1991) Determination of Radium isotope ratios and abundances in geologica samples by thermal ionization mass spectrometry. Anal Chem 63 916-919 Volpe AM, Goldstein SJ (1993) Ra- °Th disequilibrium in axial and off-axis mid-ocean ridge basalts. Geochim Cosmochim Acta 57 1233-1241... 

Barrie, A., Bricout, J. and Koziet, J. (1984) Gas chromatography stable isotope ratio analysis at natural abundance levels. Biomedical Mass Spectrometry 11, 439 447. 

McCullagh, J. S. O., Juchelka, D. and Hedges, R. E. M. (2006) Analysis of amino acid 13C abundance from human and faunal bone collagen using liquid chromatography/isotope ratio mass spectrometry. Rapid Communications in Mass Spectrometry 20, 2761 2768. 

Metges, C. C. and Petzke, K. J. (1997) Measurement of 15N/14N isotopic composition in individual plasma free amino acids of human adults at natural abundance by gas chromatography combustion isotope ratio mass spectrometry. Analytical Biochemistry 247, 158 164. 

For many applications in geochemistry and archaeology, the information desired from mass spectrometry is a precise measure of the abundance ratio of two or more isotopes of the same element - 12C/13C, or 160/180, or 206Pb/207Pb and 208Pb/207Pb at the heavier end of the mass scale. In these... 

Stable-isotope dilution analysis is an analytical technique in which a known quantity of a stable-labelled isotope is added to a sample prior to extraction, in order to quantitate a particular compound. The ratio of the naturally abundant and the stable-labelled isotope is a measure of the naturally abundant compound and can be determined only by gas chromatography-mass spectrometry since the naturally abundant and the stable-labelled isotope cannot be completely separated gas chromatographically. 

The isotope dilution gas chromatography-mass spectrometry method described by Lopez-Avila et al. [16] and discussed in section 5.3.1.3 has been applied to the determination of Atrazine in soil. In this method known amounts of labelled Atrazine were specked into soil samples before extraction with acetone-hexane. The ratio of the naturally abundant compound and the stable-labelled isotope was determined by high-resolution gas chromatography-mass spectrometry with the mass spectrometer in the selected ion monitoring mode. Detection limits of 0.1-l.Oppb were achieved. Accuracy was >86% and precision better than 8%. 

Deuterium nmr spectroscopy has been utilized for the last decade to determine large (primary deuterium) KIEs in reactions with isotopes present at the natural abundance level (Pascal et al., 1984,1986 Zhang, 1988). A great advantage of this approach is that labelled materials do not have to be synthesized. Neither is there any need for selective degradation procedures, which are often necessary to produce the molecules of low mass, e.g. C02, acceptable for isotope ratio mass spectrometry. Moreover, the KIEs for several positions can be determined from one sample. However, until quite recently the relatively low precision of the nmr integrations that are used for the quantitative assessment of the amount of deuterium at specific molecular sites has limited the applicability of this technique for determining small (secondary deuterium) KIEs. 

Figure 7. A few examples of isotopic patterns of Ne, Ti and heavy elements in SiC and graphite grains are displayed. Absolute ratios are plotted for Ne (a) whereas abundance ratios relative to solar wind composition are plotted for Kr (c) and Xe (f). The remaining elements are plotted as %o deviations from laboratory standards. The data have been obtained on bulk SiC separates by traditional mass spectrometry for Ne (Jungck and Eberhardt 1979), Kr (Ott et al. 1988 Lewis et al. 1994), Sr, Ba (Ott and Begemann 1990 Prombo et al. 1993) and Nd (Richter 1995). SIMS techniques (caption continued on facing page)...

---