The decay scheme in which rhenium-187 is transformed to osmium-187 shows promise as a means of studying mantle–crust evolution and the evolution of ore deposits. Osmium is strongly concentrated in the mantle and extremely depleted in the crust, so that crustal osmium must have exceedingly high radiogenic-to-stable ratios while the mantle values are low. In fact, crustal levels are so low that they are extremely difficult to measure with current technology. Most work to date has centred around rhenium- or osmium-enriched minerals. Because rhenium and osmium are both siderophilic (having an affinity for iron) and chalcophilic (having an affinity for sulfur), the greatest potential for this method is in studies concerning the origin and age of sulfide ore deposits.
Potassium–argon methods
The radioactive decay scheme involving the breakdown of potassium of mass 40 (40K) to argon gas of mass 40 (40Ar) formed the basis of the first widely used isotopic dating method. Since radiogenic argon-40 was first detected in 1938 by the American geophysicist Lyman T. Aldrich and A.O. Nier, the method has evolved into one of the most versatile and widely employed methods available. Potassium is one of the 10 most abundant elements that together make up 99 percent of Earth’s crust and is therefore a major constituent of many rock-forming minerals. In fact, potassium-40 decays to both argon-40 and calcium-40, but, because argon is absent in most minerals while calcium is present, the argon produced is easier to detect and measure. Most of the argon in Earth’s atmosphere has been created by the decay of potassium-40, as the argon-40 abundance is about 1,000 times higher than expected from cosmic abundances. Argon dating involves a different technology from all the other methods so far described, because argon exists as a gas at room temperature. Thus, it can be purified as it passes down a vacuum line by freezing out or reacting out certain contaminants. It is then introduced into a mass spectrometer through a series of manual or computer-controlled valves. Technical advances, including the introduction of the argon-40–argon-39 method and laser heating, that have improved the versatility of the method are described below.
In conventional potassium–argon dating, a potassium-bearing sample is split into two fractions: one is analyzed for its potassium content, while the other is fused in a vacuum to release the argon gas. After purification has been completed, a spike enriched in argon-38 is mixed in and the atomic abundance of the daughter product argon-40 is measured relative to the argon-38 added. The amount of the argon-36 present is then determined relative to argon-38 to provide an estimate of the background atmospheric correction. In this case, relatively large samples, which may include significant amounts of alteration, are analyzed. Since potassium is usually added by alteration, the daughter–parent ratio and the age might be too low.
A method designed to avoid such complexities was introduced by American geochronologist Craig M. Merrihue and English geochronologist Grenville Turner in 1966. In this technique, known as the argon-40–argon-39 method, both parent and daughter can be determined in the mass spectrometer as some of the potassium atoms in the sample are first converted to argon-39 in a nuclear reactor. In this way, the problem of measuring the potassium in inhomogeneous samples is eliminated and smaller amounts of material can be analyzed. An additional advantage then becomes possible. The sample can be heated in stages at different temperatures and the age calculated at each step. If alteration is evident, the invalid low-temperature age can be eliminated and a valid high-temperature age determined. In some cases, partly reset systems also may be detected.
As in all dating systems, the ages calculated can be affected by the presence of inherited daughter products. In a few cases, argon ages older than that of Earth which violate local relative age patterns have even been determined for the mineral biotite. Such situations occur mainly where old rocks have been locally heated, which released argon-40 into pore spaces at the same time that new minerals grew. Under favourable circumstances the isochron method may be helpful, but tests by other techniques may be required. For example, the rubidium–strontium method would give a valid isotopic age of the biotite sample with inherited argon.
As techniques evolved, argon background levels have been reduced and the method has become more and more sensitive. Capitalizing on this, it is now possible to measure the minute amount of argon released when a single spot on a crystal is heated by an intense laser beam. For geologically old potassium-rich materials, a single spot may produce sufficient gas for analysis, whereas single millimetre-sized grains (1 mm equals 0.04 inch) may be required in very young materials. Progressive refinement of the method has made new areas of research possible, and the ability to understand complexities encountered in earlier investigations has increased. In one study the age of volcanic ash as young as 215,000 ± 4,000 years and the presence of inherited older grains in another ash sample were thoroughly documented. This was done by melting single millimetre-sized grains with a laser and measuring individual argon-40–argon-39 ages with a highly sensitive gas mass spectrometer.
The potassium–argon method has provided a great deal of information about Earth’s recent and ancient past. It has been instrumental, for example, in determining the ages of the stripes of alternating normally and reversely magnetized volcanic rocks that parallel the axis of the mid-oceanic ridges. In ancient shield areas large segments of crust that were uplifted and cooled at the same time—i.e., geologic provinces—have been identified by the potassium–argon method. The technique is highly responsive to thermal events in a relatively predictable fashion, so the cooling history of a region may be established.
Thomas Edvard KroghFission-track dating
This is a special type of dating method that makes use of a microscope rather than a mass spectrometer and capitalizes on damaged zones, or tracks, created in crystals during the spontaneous fission of uranium-238. In this unique type of radioactive decay, the nucleus of a single parent uranium atom splits into two fragments of similar mass with such force that a trail of crystal damage is left in the mineral. Immersing the sample in an etching solution of strong acid or base enlarges the fission tracks into tube-shaped holes large enough to be seen under a high-powered microscope. The number of tracks present can be used to calculate the age of the sample if the uranium content is known. Fortunately, the uranium content of precisely the spot under scrutiny can be obtained by a similar process when working with a polished crystal surface. The sample is bombarded with slow (thermal) neutrons in a nuclear reactor, resulting in induced fission of uranium-235 (as opposed to spontaneous fission of uranium-238). The fission tracks produced by this process are recorded by a thin plastic film placed against the surface of the sample. The uranium content of the material can then be calculated so long as the neutron dose is known. The age of the sample is obtained using the equation, age = N × Ds/Di × 6 × 10−8, in which N is the total neutron dose expressed as neutrons per square centimetre and Ds is the observed track density for spontaneous fission while Di is that for induced fission.
The preservation of crystal damage (i.e., the retention of fission tracks) is highly sensitive to temperature and varies from mineral to mineral. The technique can be used to determine mild thermal events as low as 100 °C (212 °F). Alternately, primary ages can be calculated if the rock was formed at the surface and cooled quickly. Under these conditions the calculated fission-track ages of two minerals with widely different annealing temperatures would be identical. The accuracy achieved depends on the number of tracks counted, so that artificial glass coloured with 10 percent uranium can be dated as soon as 30 years after manufacture. With uranium levels of a few parts per million, samples as young as 300,000 years can be dated by counting tracks for one hour. When dealing with very old materials, high-uranium samples must be avoided because there are so many interlocking tracks that they can no longer be counted.
A special feature of fission-track dating lies in its ability to map the uranium distribution within mineral grains. In a uranium map for single zircon grains, the outer zones that grew during a major melting event contained much more uranium than the grains originally present. The uranium–lead age was highly biased toward the younger event, and the primary age could be determined only after the outer zones were removed. In practice, fission-track dates are regarded as cooling ages unless proved otherwise. It might also be noted that uncertainties in results may arise from an uneven distribution of uranium, statistical errors in counting, and inaccurate estimates of neutron flux (dose of neutrons).
Fission-track dating can be used on a wide variety of minerals found in most geologic materials, and it is relatively inexpensive to apply. Because closure temperatures vary widely from, say, 300 °C for titanite and zircon to less than 100 °C for biotite and apatite, valuable information can be obtained regarding the uplift and cooling rates of crustal rocks.
