Noble Gases
Abstract
The noble gases are the group of elements - helium, neon, argon, krypton, xenon - in the rightmost column of the periodic table of the elements, those which have "filled" outermost shells of electrons (two for helium, eight for the others). This configuration of electrons results in a neutral atom that has relatively low electron affinity and relatively high ionization energy. In consequence, in most natural circumstances these elements do not form chemical compounds, whence they are called "noble." Similarly, much more so than other elements in most circumstances, they partition strongly into a gas phase (as monatomic gas), so that they are called the "noble gases" (also, "inert gases"). (It should be noted, of course, that there is a sixth noble gas, radon, but all isotopes of radon are radioactive, with maximum half-life a few days, so that radon occurs in nature only because of recent production in the U-Th decay chains. The factors that govern the distribution of radon isotopes are thus quite different from those for the five gases cited. There are interesting stories about radon, but they are very different from those about the first five noble gases, and are thus outside the scope of this chapter.)In the nuclear fires in which the elements are forged, the creation and destruction of a given nuclear species depends on its nuclear properties, not on whether it will have a filled outermost shell when things cool off and nuclei begin to gather electrons. The numerology of nuclear physics is different from that of chemistry, so that in the cosmos at large there is nothing systematically special about the abundances of the noble gases as compared to other elements. We live in a very nonrepresentative part of the cosmos, however. As is discussed elsewhere in this volume, the outstanding generalization about the geo-/cosmochemistry of the terrestrial planets is that at some point thermodynamic conditions dictated phase separation of solids from gases, and that the Earth and the rest of the inner solar were made by collecting the solids, to the rather efficient exclusion of the gases. In this grand separation the noble gases, because they are noble, were partitioned strongly into the gas phase. The resultant generalization is that the noble gases are very scarce in the materials of the inner solar system, whence their common synonym "rare gases."This scarcity is probably the most important single feature to remember about noble-gas cosmochemistry. As illustration of the absolute quantities, for example, a meteorite that contains xenon at a concentration of order 10 -10 cm3STP g -1 (4×10-15 mol g-1) would be considered relatively rich in xenon. Yet this is only 0.6 ppt (part per trillion, fractional abundance 10-12) by mass. In most circumstances, an element would be considered efficiently excluded from some sample if its abundance, relative to cosmic proportions to some convenient reference element, were depleted by "several" orders of magnitude. But a noble gas would be considered to be present in quite high concentration if it were depleted by only four or five orders of magnitude (in the example above, 10-10 cm3STP g-1 of xenon corresponds to depletion by seven orders of magnitude), and one not uncommonly encounters noble-gas depletion of more than 10 orders of magnitude.The second most important feature to note about noble-gas cosmochemistry is that while a good deal of the attention given to noble gases really is about chemistry, traditionally a good deal of attention is also devoted to nuclear phenomena, much more so than for most other elements. This feature is a corollary of the first feature noted above, namely scarcity. A variety of nuclear transmutation processes - decay of natural radionuclides and energetic particle reactions - lead to the production of new nuclei that are often new elements. Most commonly, the quantity of new nuclei originating in nuclear transmutation is very small compared to the quantity already present in the sample in question, metaphorically a drop in the bucket. Thus, they are very difficult or impossible to detect and, therefore, in practical terms, attracting little or no interest. When the bucket is empty, or nearly so, however, the "drop" contributed by nuclear transmutations may become observable or even dominant. Traditionally there are two types of (nearly) empty buckets that are most suitable for revealing the effects of nuclear transmutations: short-lived radionuclides (e.g., 10Be and 26Al) which would be entirely absent except for recent nuclear reactions, and the noble gases, renowned for their scarcity.Emphasis on nuclear processes explains what sometimes seems to be an obsession with isotopes in noble-gas geo- and cosmochemistry. Different nuclear processes will produce different isotopes, singly or in suites with well-defined proportions (i.e., "components"), different from one process to another. Much of the traditional agenda of noble-gas geochemistry, and especially cosmochemistry, thus consists of isotopic analysis, and deconvolution of an observed isotopic spectrum into constituent components. (In most geochemical investigations, noble gases are detected by mass spectrometry, a technique that is inherently sensitive to specific isotopes, not just the chemical element. Isotopic data thus emerge naturally in most studies. Noble-gas mass spectrometry can be a much more sensitive technique than other traditional types of mass spectrometry because the gases are "noble," and therefore relatively easy to separate from other elements, and because they are scarce, so that they can be analyzed in "static"-mode (no pumping during analysis) gas-source spectrometers, permitting relatively high detection efficiency without overwhelming blanks.) In realistic terms, it is very difficult to appreciate noble-gas geo-/cosmochemistry without a basic familiarity with noble-gas isotopes: which isotopes occur in nature (i.e., which are stable), in what approximate abundance they are found, how they relate to non-noble neighbors, and, to some extent, how they are associated with specific nuclear processes. Figure 1 provides assistance in this regard. (6K)Figure 1. A display of the isotopes of the noble gases and neighboring isotopes in the familiar "chart of the nuclides" format. The abscissa is neutron number (N) and the ordinate is proton number (Z). The box corresponding to any pair (Z, N) represents an isotope; an element is represented by a horizontal row. Boxes for stable isotopes are shown with solid outline; for the noble gases, approximate solar (in the case of He, protosolar) isotope ratios are shown at the bottom of each box. Selected unstable isotopes are shown as boxes with broken line edges. The left-superscript isotope label is the atomic weight A (=Z+N). The five panels show regions around the five noble gases (excluding Rn). When the goal is to identify and quantify different noble-gas components that may be present in a sample or group of samples, a common approach to this goal is to try to unmix the components, at least partially, to provide some leverage. One path to this end, of course, is analysis of different samples that may contain the components in different proportions, and thus have different isotopic compositions. Another path, available in addition to or instead of the first, is stepwise heating analysis, which has traditionally been very extensively used in noble-gas studies. Noble gases may be released from solid samples by volume diffusion, or by reaction, recrystallization, melting, or even evaporation of their host phases. If different noble-gas components reside in physically distinct locations within a complex sample, they may be liberated, and thus become available for analysis, at different steps in a time-temperature heating sequence. Differential release of isotopically distinct components will then result in variation of the isotopic composition of gas released in different steps (e.g., see Figures 2 and 4). (12K)Figure 2. A three-isotope diagram illustrating compositional variations in lunar samples and meteorites, as observed in stepwise in vacuo etching and pyrolysis. Since the observed isotopic compositions do not lie on a single straight line, at least three isotopically distinct components must contribute in variable proportions. These data are interpreted as superposition of solar wind (SW), solar energetic particles (SEP), and galactic cosmic ray, i.e., spallation (GCR) Ne components (source Wieler, 1998). A common tool for visualization of isotopic variations is the so-called "three-isotope diagram," in which two isotope ratios, each with the same reference (denominator) isotope, are displayed on abscissa and ordinate (e.g., Figure 2). Two isotopically distinct components will plot at distinct points on a three-isotope diagram, and an often-used feature is that mixtures of the two components will plot on the straight line joining those two points. A lever rule applies: the greater the proportion that one component contributes to a mixture, the closer the point representing the mixture will lie to the point representing that end-member component, and there is a linear relationship between fractional distance from one end-member to the other and the fraction that each component contributes to the mixture (specifically to the reference isotope). If observed isotopic data are variable but the variations in two ratios are correlated, so as to be consistent with a straight line on a three-isotope diagram, it can be inferred that at least two components are present and it will often be hypothesized that only two components are present, in which case their compositions can be constrained to lie on the line, one on either side of the data field. If three components are present, not coincidentally collinear on this diagram, mixtures will occupy the triangular field defined by the three compositions, and conversely if observed data are not consistent with linear correlation it can be inferred that at least three components are contributing to the mix. The concept of the three-isotope diagram is readily generalized. Four isotopes defining three ratios (all with the same reference isotope), for example, will define a three-dimensional space in which mixture of two components will produce compositions lying along a straight line, and mixture of three components will produce compositions lying in a plane, etc. Generalization to more dimensions is mathematically straightforward, even if difficult to envision.
- Publication:
-
Treatise on Geochemistry
- Pub Date:
- December 2003
- DOI:
- 10.1016/B0-08-043751-6/01066-5
- Bibcode:
- 2003TrGeo...1..381P