Natural Isotopic Composition of the Elements

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... 

Relative Atomic Masses and Natural Isotopic Composition of the Elements... 

The 1981 report on atomic weights includes a complete review of the natural isotopic composition of the elements and also tabulates the relative atomic masses for selected radioisotopes. This information is required for the conversion of spectroscopic data from that corresponding to specific isotopes to the naturally occurring isotopic abundance. 

The atomic mass given refers to the natural isotopic composition of the element except for hydrogen and deuterium where the mass is that of the isotopes H and respectively. 

Because in nature the ground state of a stable nuclide is often attained by decay chains involving intermediate species decaying at different rates, it is worth evaluating the implications of the relative magnitudes of the various decay constants on the isotopic composition of the element. 

I he atomic wcighi varies because of natural variations in the isotopic composition of the element, caused by the various isotopes having different origins - I h is the end product of the thorium decay scries, while Ph and " Pb arise Irom uranium as end products of the actinium and radium series respectively. Lead-204 has no existing natural radioactive precursors. Electronic configuration l.v 2s lfc22/j"3v 3//,3i/l"4v- 4/, 4l/" 4/ IJ5v- 5/ "5t/l"bv />-. Ionic radius Pb I.IX A. Pb 1 0.7(1 A. Metallic radius 1.7502 A. Covalent radius (ip i 1.44 A. First ionization potential 7.415 cV second. 14.17 eV. Oxidation... 

The activity of naturally radioactive elements is a measure of their mass. Prerequisites of application of the correlation between mass and activity according to eq. (17.1) are that the isotopic composition of the element to be determined is constant and that interfering radioactive impurities are absent. If the daughter nuelides are also radioactive, radioactive equilibrium must be established or the daughter nuclides must be separated off quantitatively. Interference of radioactive impurities may be avoided by measuring the a or y spectrum of the radionuclide considered. 

The measurement of isotopic abundances began early this century following the discovery of neon isotopes by J.J. Thompson in 1912. F.W. Aston developed the mass spectrometer into a quantitative instrument for measuring isotopic abundances and by 1935 the isotopic composition of most elements was known. The first International Table of Stable Isotopes was drawn up in 1936, while the latest table of Isotopic Compositions of the Elements appeared recently (4). Lead is an element for which there was early evidence of natural variations in its isotopic composition (5) these were ultimately used to measure the age of the Earth (6). Natural variations have been reported in 43 other elements although many relate to exceptional samples. There are 18 elements in which variations are not uncommon, although most of these elements have relatively light atoms with atomic numbers less than 16 (4). 

The atomic mass varies because of natural variations in the isotopic composition of the element. The observed ranges are boron. 0.00.1 carbon. 0.00005 hydrogen. 0.00001 oxygen, 0.0001 silicon. 0.001 sulfur, 0.003. 

The isotope composition of the elements is mainly obtained from the Berkeley database [1.15]. For elements in general only naturally occurring isotopes, stable and radioactive, have been reported in detail. For the radioactive elements, without stable isotopes, the most long-lived isotopes have been described. 

FIGURE 2.5 Relative abundance of the naturally occurring isotopes of the elements. (From UIPAC Isotopic Composition of the Elements, Pure and Applied Chemistry 75[6], 683-799, 2003.)... 

The composition of the Earth was determined both by the chemical composition of the solar nebula, from which the sun and planets formed, and by the nature of the physical processes that concentrated materials to form planets. The bulk elemental and isotopic composition of the nebula is believed, or usually assumed to be identical to that of the sun. The few exceptions to this include elements and isotopes such as lithium and deuterium that are destroyed in the bulk of the sun s interior by nuclear reactions. The composition of the sun as determined by optical spectroscopy is similar to the majority of stars in our galaxy, and accordingly the relative abundances of the elements in the sun are referred to as "cosmic abundances." Although the cosmic abundance pattern is commonly seen in other stars there are dramatic exceptions, such as stars composed of iron or solid nuclear matter, as in the case with neutron stars. The... 

A few elements, among them fluorine and phosphoras, occur naturally with just one isotope, but most elements are isotopic mixtures. For example, element number 22 is titanium (Ti), a light and strong metal used in Jet engines and in artificial human Joints. There are five naturally occurring isotopes of Ti. Each one has 22 protons in its nuclei, but the number of neutrons varies from 24 to 28. In a chemical reaction, all isotopes of an element behave nearly identically. This means that the isotopic composition of an element remains essentially constant. The isotopic composition of Ti (number percentages) is... 

For purposes of chemical bookkeeping, it is unnecessary to know the isotopic molar masses and isotopic distributions of the elements. All we need to know is the mass of one mole of an element containing its natural composition of isotopes. These molar masses usually are included in the periodic table, and they appear on the inside front and back covers of this textbook. 

James et al. (2003) performed laboratory experiments in which aqueous fluids were reacted with natural samples of unaltered MORE (5 Li = +4.6) and a quartzofeldspathic mud/turbidite mixture (5 Li = +1.3). The starting fluids had elemental compositions generally intermediate between seawater and hydrothermal fluids, and were isotopically light (5 Li = -5.5). The initial fluid/solid was 4. Fluid samples were extracted as the experiments were raised to 350°C over 400-500 h, and then during cooling (c. 740 h total). In both experiments Li was removed from solution at low temperatures, but the isotopic composition of the fluids... 

Richter FM, Davis AM, Ehel DS, Hashimoto A (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions Experiments, theoretical considerations, and constraints on their thermal evolution. Geochim Cosmochim Acta 66 521-540 Richter FM, Davis AM, DePaolo DJ, Watson EB (2003) Isotope fractionation by chemical diffusion between molten basalt and rhyolite. Geochim Cosmochim Acta 67 3905-3923 Rudnick RL, Fountain DM (1995) Nature and composition of the continental crust—a lower crustal perspective. Rev Geophys 33 267-309... 

Table A. 1 comprises the stable elements from hydrogen to bismuth with the radioactive elements technetium and promethium omitted. Natural variations in isotopic composition of some elements such as carbon or lead do not allow for more accurate values, a fact also reflected in the accuracy of their relative atomic mass. However, exact masses of the isotopes are not affected by varying abundances. The isotopic masses listed may differ up to some 10 u in other publications.

A key problem in the present natural analogue study is the distinction between chemical variations related to trace element migration during basalt alteration and variations due to magmatic fractionation and other syn-intrusive processes. The detailed evaluation of the available data has shown that the chemical and isotopic composition of the HC1 residues is largely controlled by fractional crystallization and syn-intrusive assimilation of salt. In contrast, the chemical composition of the leachates is strongly modified by post-intrusive alteration (Steinmann et al. 1999). 

Standard states. The standard or reference state of each of the elemental substances is taken to be that physical state (or one of them, if there are two or more) in which the element naturally exists at a pressure, or a fugacity, of one atmosphere and at a temperature of 18°. The isotopic composition of each element in its standard state is understood to be the naturally existing one. For the element carbon, we have selected its form as diamond, C (c, diamond), as the standard state because no other form of solid carbon is at present a reproducible and invariable one. 

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