Isotopes, stable natural abundancies

Symbol Ar atomic number 18 atomic weight 39.948 an inert gas element electronic configuration Is22s22p63s23p ionization potential 15.76eV stable isotopes and natural abundance Ar-40 99.6%, Ar-36 0.337%, Ar-38 0.063% unstable isotopes, half-life and disintegration mode ... 

This example illustrates how m/e values of ions that differ only in isotopic composition can be used to determine elemental compositions. The important isotopes for this purpose in addition to those of chlorine are the stable isotopes of natural abundance, 13C (1.1%), 15N (0.37%), 170 (0.04%), lsO (0.20%). As a further example, suppose that we have isolated a hydrocarbon and have determined from its mass spectrum that M + = 86 mass units. In the absence of any combination reactions there will be an (M + 1)+ ion corresponding to the same molecular ion but with one 13C in place of 12C. The intensity ratio (M + 1 )+/M+ will depend on the number of carbon atoms present, because the more carbons there are the greater the probability will be that one of them is 13C. The greater the probability, the larger the (M + 1 )+/M+ ratio. For n carbons, we expect... 

Element Most abundant mass (100%) Stable isotope Relative natural abundance (%)... 

Antimony is a metalloid and its presence in the environment is increasing owing to extensive anthropogenic utilization. The toxicity of antimony depends on its chemical form, and the main species of interest include Sb(III), Sb(V), mono-methylstibonic acid, and dimethylstibonic acid. Sb has two stable naturally abundant isotopes, Sb and Sb, with natural relative abundances of 57.2 and 42.8%, respectively. 

Figrue BTl 1.1 shows the range of radiolfequencies where resonances may be expected, between 650 and 140 MHz, when Bq = 14.1 T, i.e. when the H resonance frequency is 600 MHz. There is one bar per stable isotope. Its width is the reported chemical shift range (Bl.11.5) for that isotope, and its height corresponds to the log of the sensitivity at the natural abundance of the isotope, covering about six orders of magnitude. The... 

Arsenic [7440-38-2J, although often referred to as a metal, is classified chemically as a nonmetal or metalloid and belongs to Group 15 (VA) of the periodic table (as does antimony). The principal valences of arsenic are +3, +5, and —3. Only one stable isotope of arsenic having mass 75 (100% natural abundance) has been observed. 

Accurate atomic weight values do not automatically follow from precise measurements of relative atomic masses, however, since the relative abundance of the various isotopes must also be determined. That this can be a limiting factor is readily seen from Table 1.3 the value for praseodymium (which has only 1 stable naturally occurring isotope) has two more significant figures than the value for the neighbouring element cerium which has 4 such isotopes. In the twelve years since the first edition of this book was published the atomic weight values of no fewer than 55 elements have been improved, sometimes spectacularly, e.g. Ni from 58.69( 1) to 58.6934(2). 

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). 

Stott, A.W., Davies, E., Evershed, R.E. and Tuross, N. 1997 Monitoring the routing of dietary and biosynthesized lipids through compound-specific stable isotope (delta C) measurements at natural abundance. Naturwissenschcften 84(2) 82-86. 

Cannes, L.Z., Martinez del Rio, C., Koch, P. (1998). Natural abundance variations in stable isotopes and their potential uses in animal physiological ecology. Comparative Biochemistry and Physiology - Part A Molecular Integrative Physiology, Vol. 119, No. 3, pp. 725-737. (http //dx.doi.org/10.1016/S1095-6433(98)01016-2)... 

The use of natural abundance variations in stable isotopes as tracers relies on the fractionations that occur during chemical, physical and biological processes (Ambrose 1993). Differences in fractionation during these processes lead to distinct isotopic signatures for biological materials, such as in foods exploited by humans in antiquity. 

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

Jim, S., Ambrose, S. H. and Evershed, R. P. (2003b) Natural abundance stable carbon isotope evidence for the routing and de novo synthesis of bone FA and cholesterol. Lipids 38, 179 186. 

Water is a mixture of varying isotopic composition (Franks, 2000). In addition to the two most common isotopes, 160 and there are two stable oxygen isotopes (170, lsO), one stable hydrogen isotope (2H, deuterium), and one radioactive hydrogen isotope (3H, tritium, half-life = 12.6 years). Water also contains low concentrations of hydronium (H30+) and hydroxide ions (OH-) and their isotopic variants. In total, water consists of more than 33 chemical variants of HOH however, these variants occur in relatively minor amounts (Fennema, 1996). Table II gives the natural abundance isotopic composition of the four major water species. 

The elements whose isotopes are routinely measured with gas inlet mass spectrometers are carbon (12C and 13C, but not 14C), oxygen (160, 170, l80), hydrogen ( H, 2H, but not 3H), nitrogen (14N and 1SN) and sulphur (32S, 33S, 34). Stable isotopes of H, C, N, O, and S occur naturally throughout atmosphere, hydrosphere, lithosphere, and biosphere. They are atoms of the same elements with a different mass. Each element has a dominant light isotope with the nominal atomic weight (I2C, 160,14N, 32S, and H) and one or two heavy isotopes (l3C, nO, 180, 15N, 33S, 34S, and, 2H) with a natural abundance of a few percent or less Table 1). 

Table 1. Natural abundance of stable isotopes (atom %) (Oebelmann et al., 2000)...

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%. 

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