The discovery of radioactivity and the radiogenic decay of isotopes in the early part of the 20th century opened the way for dating rocks by an absolute, rather than relative, method. Up to this time estimates of the age of the Earth had been based on assumptions about rates of evolution, rates of deposition, the thermal behaviour of the Earth and the Sun or interpretation of religious scriptures. Radiometric dating uses the decay of isotopes of elements present in minerals as a measure of the age of the rock: to do this, the rate of decay must be known, the proportion of different isotopes present when the mineral formed has to be assumed, and the proportions of different isotopes present today must be measured. This dating method is principally used for determining the age of formation of igneous rocks, including volcanic units that occur within sedimentary strata. It is also possible to use it on authigenic minerals, such as glauconite, in some sedimentary rocks. Radiometric dating of minerals in metamorphic rocks usually indicates the age of the metamorphism.
Radioactive decay series
A number of elements have isotopes (forms of the element that have different atomic masses) that are unstable and change by radioactive decay to the isotope of a different element. Each radioactive decay series takes a characteristic length of time known as the radioactive half-life, which is the time taken for half of the original (parent) isotope to decay to the new (daughter) isotope. The decay series of most interest to geologists are those with half-lives of tens, hundreds or thousands of millions of years. If the proportions of parent and daughter isotopes of these decay series can be measured, periods of geological time in millions to thousands of millions of years can be calculated.
To calculate the age of a rock it is necessary to know the half-life of the radioactive decay series, the amount of the parent and daughter isotopes present in the rock when it formed, and the present proportions of these isotopes. It must also be assumed that all the daughter isotope measured in the rock today formed as a result of decay of the parent. This may not always be the case because addition or loss of isotopes can occur during weathering, diagenesis and metamorphism and this will lead to errors in the calculation of the age. It is therefore important to try to ensure that decay has taken place in a 'closed system', with no loss or addition of isotopes, by using only unweathered and unaltered material in analyses. The radiometric decay series commonly used in radiometric dating of rocks are detailed in the following sections. The choice of method of determination of the age of the rock is governed by its age and the abundance of the appropriate elements in minerals.
Practical radiometric dating
The samples of rock collected for radiometric dating are generally quite large (several kilograms) to eliminate inhomogeneities in the rock. The samples are crushed to sand and granule size, thoroughly mixed to homogenise the material and a smaller subsample selected. In cases where particular minerals are to be dated, these are separated from the other minerals by using heavy liquids (liquids with densities similar to that of the minerals) in which some minerals will float and others sink, or magnetic separation using the different magnetic properties of minerals. The mineral concentrate may then be dissolved for isotopic or elemental analysis, except for argon isotope analysis, in which case the mineral grains are heated in a vacuum and the composition of the argon gas driven off is measured directly. Measurement of the concentrations of different isotopes is carried out with a mass spectrometer. In these instruments a small amount (micrograms) of the sample is heated in a vacuum to ionise the isotopes and these charged particles are then accelerated along a tube in a vacuum by a potential difference. Part-way along the tube a magnetic field induced by an electromagnet deflects the charged particles. The amount of deflection will depend upon the atomic mass of the particles so different isotopes are separated by their different masses. Detectors at the end of the tube record the number of charged particles of a particular atomic mass and provide a ratio of the isotopes present in a sample.
Potassium–argon and argon–argon dating
This is the most widely used system for radiometric dating of sedimentary strata, because it can be used to date the potassium-rich authigenic mineral glauconite and volcanic rocks (lavas and tuffs) that contain potassium in minerals such as some feldspars and micas. One of the isotopes of potassium, 40 K, decays partly by electron capture (a proton becomes a neutron) to an isotope of the gaseous element argon, 40 Ar, the other product being an isotope of calcium, 40 Ca. The half-life of this decay is 11.93 billion years. Potassium is a very common element in the Earth’s crust and its concentration in rocks is easily measured. However, the proportion of potassium present as 40 K is very small at only 0.012%, and most of this decays to 40 Ca, with only 11% forming 40 Ar. Argon is an inert rare gas and the isotopes of very small quantities of argon can be measured by a mass spectrometer by driving the gas out of the minerals. K–Ar dating has therefore been widely used in dating rocks but there is a significant problem with the method, which is that the daughter isotope can escape from the rock by diffusion because it is a gas. The amount of argon measured is therefore commonly less than the total amount produced by the radioactive decay of potassium. This results in an underestimate of the age of the rock. The problems of argon loss can be overcome by using the argon–argon method. The first step in this technique is the irradiation of the sample by neutron bombardment to form 39 Ar from 39 K occurring in the rock. The ratio of 39 K to 40 K is a known constant so if the amount of 39 Ar produced from 39 K can be measured, this provides an indirect method of calculating the 40 K present in the rock. Measurement of the 39 Ar produced by bombardment is made by mass spectrometer at the same time as measuring the amount of 40 Ar present. Before an age can be calculated from the proportions of 39 Ar and 40 Ar present it is necessary to find out the proportion of 39 K that has been converted to 39 Ar by the neutron bombardment. This can be achieved by bombarding a sample of known age (a 'standard') along with the samples to be measured and comparing the results of the isotope analysis. The principle of the Ar–Ar method is therefore the use of 39 Ar as a proxy for 40 K. Although a more difficult and expensive method, Ar–Ar is now preferred to K–Ar. The effects of alteration can be eliminated by step-heating the sample during determination of the amounts of 39 Ar and 40 Ar present by mass spectrometer. Alteration (and hence 40 Ar loss) occurs at lower temperatures than the original crystallisation so the isotope ratios measured at different temperatures will be different. The sample is heated until there is no change in ratio with increase in temperature (a 'plateau' is reached): this ratio is then used to calculate the age. If no 'plateau' is achieved and the ratio changes with each temperature step the sample is known to be too altered to provide a reliable date.
Other radiometric dating systems
Rubidium–strontium dating
This is a widely used method for dating igneous rocks because the parent element, rubidium, is common as a trace element in many silicate minerals. The isotope 87 Rb decays by shedding an electron (beta decay) to 87 Sr with a half-life of 48 billion years. The proportions of two of the isotopes of strontium, 86 Sr and 87 Sr, are measured and the ratio of 86 Sr to 87 Sr will depend on two factors. First, this ratio will depend on the proportions in the original magma: this will be constant for a particular magma body but will vary between different bodies. Second, the amount of 87 Sr present will vary according to the amount produced by the decay of 87 Rb: this depends on the amount of rubidium present in the rock and the age. The rubidium and strontium concentrations in the rock can be measured by geochemical analytical techniques such as XRF (X-ray fluorescence). Two unknowns remain: the original 86 Sr/87 Sr ratio and the 87 Sr formed by decay of 87 Rb (which provides the information needed to determine the age). The principle of solving simultaneous equations can be used to resolve these two unknowns. If the determination of the ratios of 86 Sr/87 Sr and Rb/Sr is carried out for two different minerals (e.g. orthoclase and muscovite), each will start with different proportions of strontium and rubidium because they are chemically different. An alternative method is whole-rock dating, in which samples from different parts of an igneous body are taken, which, if they have crystallised at different times, will contain different amounts of rubidium and strontium present. This is more straightforward than dating individual minerals as it does not require the separation of these minerals.
Uranium–lead dating
Isotopes of uranium are all unstable and decay to daughter elements that include thorium, radon and lead. Two decays are important in radiometric dating: 238 U to206 Pb with a half-life of 4.47 billion years and 235 U to 207 Pb with a half-life of 704 million years. The naturally occurring proportions of 238 U and 235 U are constant, with the former the most abundant at 99% and the latter 0.7%. By measuring the proportions of the parent and daughter isotopes in the two decay series it is possible to determine the amount of lead in a mineral produced by radioactive decay and hence calculate the age of the mineral. Trace amounts of uranium are to be found in minerals such as zircon, monazite, sphene and apatite: these occur as accessory minerals in igneous rocks and as heavy minerals in sediments. Dating of zircon grains using uranium–lead dating provides information about provenance of the sediment. Dating of zircons has been used to establish the age of the oldest rocks in the world. Other parts of the uranium decay series are used in dating in the Quaternary.
Samarium–neodymium dating
These two rare earth elements in this decay series are normally only present in parts per million in rocks. The parent isotope is 147 Sm and this decays by alpha particle emission to 143 Nd with a half-life of 106 billion years. The slow generation of 143 Nd means that this technique is best suited to older rocks as the effects of analytical errors are less significant. The advantage of using this decay series is that the two elements behave almost identically in geochemical reactions and any alteration of the rock is likely to affect the two isotopes to equal degrees. This eliminates some of the problems encountered with Rb–Sr caused by the different reactivity and mobility of the two elements in the decay series. This dating technique has been used on sediments to provide information about the age of the rocks that the sediment was derived from: different provenance areas, for example continental cratons of different ages, can be distinguished by analysis of mud and mudstones.
Rhenium–osmium dating
Rhenium occurs in low concentrations in most rocks, but its most abundant naturally occurring isotope 187 Re undergoes beta decay to an isotope of osmium 187 Os with a half-life of 42 Ga. This dating technique has been used mainly on sulphide ore bodies and basalts, but there have also been some successful attempts to date the depositional age of mudrocks with a high organic content. Osmium isotopes in seawater have also been shown to have varied through time.
Applications of radiometric dating
Radiometric dating is the only technique that can provide absolute ages of rocks through the stratigraphic record, but it is limited in application by the types of rocks which can be dated. The age of formation of minerals is determined by this method, so if orthoclase feldspar grains in a sandstone are dated radiometrically, the date obtained would be that of the granite the grains were eroded from. It is therefore not possible to date the formation of rocks made up from detrital grains and this excludes most sandstones, mudrocks and conglomerates. Limestones are formed largely from the remains of organisms with calcium carbonate hard parts, and the minerals aragonite and calcite cannot be dated radiometrically on a geological time scale. Hence almost all sedimentary rocks are excluded from this method of dating and correlation. An exception to this is the mineral glauconite, an authigenic mineral that forms in shallow marine environments: glauconite contains potassium and may be dated by K–Ar or Ar–Ar methods, but the mineral is readily altered and limited in occurrence. The formation of igneous rocks usually can be dated successfully provided that they have not been severely altered or metamorphosed. Intrusive bodies, including dykes and sills, and the products of volcanic activity (lavas and tuff) may be dated and these dates used to constrain the ages of the rocks around them by the laws of stratigraphic relationships. Dates from metamorphic rocks may provide the age of metamorphism, although complications can arise if the degree of metamorphism has not been high enough to reset the radiometric 'clock', or if there have been multiple phases of metamorphism. General stratigraphic relations and isotopic ages are the principal means of correlating intrusive igneous bodies. Geographically separate units of igneous rock can be shown to be part of the same igneous suite or complex by determining the isotopic ages of the rocks at each locality. Radiometric dating can also be very useful for demonstrating correspondence between extrusive igneous bodies. The main drawbacks of correlation by this method are the limited range of lithologies that can be dated and problems of precision of the results, particularly with older rocks. For example, if two lava beds were formed only a million years apart and there is a margin of error in the dating methods of one million years, correlation of a lava bed of unknown affinity to one or the other cannot be certain.
