Abundance ratio, isotope

The possibility that an even larger impact caused the P T extinction received support when Becker and Poreda found that helium and argon atoms were present in the inner cores of some of the fullerenes from the P T boundary sediments (The cover of this book shows a helium atom inside a mol ecule of Ceo) What is special about the fullerene trapped atoms is that the mixtures of both helium and argon isotopes resemble extraterrestrial isotopic mixtures more than earthly ones The He/ He ratio in the P T boundary fullerenes for example is 50 times larger than the natural abundance ratio... 

In a process similar to that described in the previous item, the stored data can be used to identify not just a series of compounds but specific ones. For example, any compound containing a chlorine atom is obvious from its mass spectrum, since natural chlorine occurs as two isotopes, Cl and Cl, in a ratio of. 3 1. Thus its mass spectrum will have two molecular ions separated by two mass units (35 -i- 2 = 37) in an abundance ratio of 3 1. It becomes a trivial exercise for the computer to print out only those scans in which two ions are found separated by two mass units in the abundance ratio of 3 1 (Figure 36.10). This selection of only certain ion masses is called selected ion recording (SIR) or, sometimes, selected ion monitoring (SIM, an unfortunate... 

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. 

The two isotopes of chlorine are Cl and y3l, which occur naturally in the abundance ratio of 3 1. 

A diagrammatic illustration of the effect of an isotope pattern on a mass spectrum. The two naturally occurring isotopes of chlorine combine with a methyl group to give methyl chloride. Statistically, because their abundance ratio is 3 1, three Cl isotope atoms combine for each Cl atom. Thus, the ratio of the molecular ion peaks at m/z 50, 52 found for methyl chloride in its mass spectrum will also be in the ratio of 3 1. If nothing had been known about the structure of this compound, the appearance in its mass spectrum of two peaks at m/z 50, 52 (two mass units apart) in a ratio of 3 1 would immediately identify the compound as containing chlorine. 

One method for measuring the temperature of the sea is to measure this ratio. Of course, if you were to do it now, you would take a thermometer and not a mass spectrometer. But how do you determine the temperature of the sea as it was 10,000 years ago The answer lies with tiny sea creatures called diatoms. These have shells made from calcium carbonate, itself derived from carbon dioxide in sea water. As the diatoms die, they fall to the sea floor and build a sediment of calcium carbonate. If a sample is taken from a layer of sediment 10,000 years old, the carbon dioxide can be released by addition of acid. If this carbon dioxide is put into a suitable mass spectrometer, the ratio of carbon isotopes can be measured accurately. From this value and the graph of solubilities of isotopic forms of carbon dioxide with temperature (Figure 46.5), a temperature can be extrapolated. This is the temperature of the sea during the time the diatoms were alive. To conduct such experiments in a significant manner, it is essential that the isotope abundance ratios be measured very accurately. 

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). 

Isotopes of an element are formed by the protons in its nucleus combining with various numbers of neutrons. Most natural isotopes are not radioactive, and the approximate pattern of peaks they give in a mass spectrum can be used to identify the presence of many elements. The ratio of abundances of isotopes for any one element, when measured accurately, can be used for a variety of analytical purposes, such as dating geological samples or gaining insights into chemical reaction mechanisms. 

Two further expressions are used in discussions on isotope ratios. These are the atom% and the atom% excess, which are defined in Figure 48.6 and are related to abundance ratios R. It has been recommended that these definitions and some similar ones should be used routinely so as to conform with the system of international units (SI). While these proposals will almost certainly be accepted by mass spectrometrists, their adoption will still leave important data in the present format. Therefore, in this chapter, the current widely used methods for comparison of isotope ratios are fully described. The recommended Sl-compatible units such as atom% excess are introduced where necessary. 

Many artificial (likely radioactive) isotopes can be created through nuclear reactions. Radioactive isotopes of iodine are used in medicine, while isotopes of plutonium are used in making atomic bombs. In many analytical applications, the ratio of occurrence of the isotopes is important. For example, it may be important to know the exact ratio of the abundances (relative amounts) of the isotopes 1, 2, and 3 in hydrogen. Such knowledge can be obtained through a mass spectrometric measurement of the isotope abundance ratio. 

Approximate ratios of isotope abundance ratios are important in identifying elements. For example, the naturally occurring Cl, Cl isotopes exist in an abundance ratio of about 3 1, and C, exist in a ratio of about 99 1. 

A 6-value is used to compare a measured isotope ratio in a sample with that for a standard substance containing the same isotopes but in known abundance ratio. 

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). 

What are the relative contributions of these two sources Two approaches have been taken. One is to establish the geology and hydrology of a basin in great detail. This has been carried out for the Amazon (Stallard and Edmond, 1981) with the result that evaporites contribute about twice as much sulfate as sulfide oxidation. The other approach is to apply sulfur isotope geochemistry. As mentioned earlier, there are two relatively abundant stable isotopes of S, and The mean 34/32 ratio is 0.0442. However, different source rocks have different ratios, which arise from slight differences in the reactivities of the isotopes. These deviations are expressed as a difference from a standard, in the case of sulfur the standard being a meteorite found at Canyon Diablo, Arizona. 

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. 

Mohler FL i960) Isotopic abundance ratios reported for reference samples stocked by the National Bureau of Standards. NBS Technical Note 51 US Dept of Commerce Wash DC. 

Quetel CR, Prohaska T, Hamester M, Kerl W, Taylor PDP (2000b) Examination of the performance exhibited by a single detector double focusing magnetic sector ICP-MS instrument for uranium isotope abundance ratio measurements over almost three orders of magnitude and down to pg g-1 concentration levels. J Anal At Spectrom 15 353-358... 

Note The nucleus of each element may have more than one neutron/proton ratio (different isotopes) in the table are presented the most abundant stable isotopes of some elements and the number before their symbols represents very approximately the mass of that isotope (mass number, A). 

The most abundant isotope of carbon has a mass of 12 atomic mass units, 12C. A less abundant stable isotope is 13C. And much less abundant is the radioactive isotope t4C, also called radiocarbon. It is convenient to express the abundances of these rare isotopes in terms of ratios of the number of atoms of the rare isotope in a sample to the number of atoms of the abundant isotope. We call this ratio r, generally a very small number. To arrive at numbers of convenient magnitude, it is conventional to express the ratio in terms of the departure of r from the ratio in a standard, which I call. v, and to express this departure in parts per thousand of s. Thus the standard delta notation is... 

In radiocarbon dating, the quantity to be measured is the ratio of the abundances of the rare isotope (14C) to that of the stable isotopes (12C, 13C). These abundance ratios are not measured on an absolute basis, but are compared to that of an internationally-accepted standard. (It is likely that a similar standard will be adopted for 10Be dating.) These measurement requirements have several consequences ... 

Fig. 5.26. Nucleosynthesis products from SN la (Fig. 5.25) and SNII (Fig. 5.12) combined in a ratio of 1 10, compared to Solar-System abundances. (A slightly higher ratio of 1 7 gives optimal fit to elemental, as opposed to individual nuclidic abundances.) Dominant isotopes of multi-isotope elements are circled. Adapted from Tsujimoto (1993).

For purposes of comparison with stellar abundances, it is useful to have the relative contributions of s- and r-processes to the various elements (as opposed to nuclides) in the Solar System, because in most cases only element abundances without isotopic ratios are available from stellar spectroscopy. At the same time, elements formed in one process may often be expected to vary by similar factors in the course of stellar and Galactic evolution, but to be found in differing ratios to elements formed in another process. Relative contributions are listed for some key elements in Table 6.3. 

McKinney, C.R., McCrea, J.M., Epstein, S., Allen, H.A., Urey, H.C. Improvements in mass spectrometers for the measurement of small differences in isotope abundance ratios. Rev. Sci. Instrum. 21,1950,724. 

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... 

Note. Not all naturally occurring isotopes are stable - some are radioactive but with long half-lives. See (for example) WebElements [http //www.webelements.com/webelements/index. html] for abundance ratios of naturally occurring isotopes and half-lives of radioisotopes. 

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