K–Ar dating

Potassium–argon dating, abbreviated K–Ar dating, is a radiometric dating method used in geochronology and archaeology. It is based on measurement of the product of the radioactive decay of an isotope of potassium (K) into argon (Ar). Potassium is a common element found in many materials, such as feldspars, micas, clay minerals, tephra, and evaporites. In these materials, the decay product ⁴⁰
Ar
is able to escape the liquid (molten) rock but starts to accumulate when the rock solidifies (recrystallizes). The amount of argon sublimation that occurs is a function of the purity of the sample, the composition of the mother material, and a number of other factors. These factors introduce error limits on the upper and lower bounds of dating, so that the final determination of age is reliant on the environmental factors during formation, melting, and exposure to decreased pressure or open air. Time since recrystallization is calculated by measuring the ratio of the amount of ⁴⁰
Ar
accumulated to the amount of ⁴⁰
K
remaining. The long half-life of ⁴⁰
K
allows the method to be used to calculate the absolute age of samples older than a few thousand years.

The quickly cooled lavas that make nearly ideal samples for K–Ar dating also preserve a record of the direction and intensity of the local magnetic field as the sample cooled past the Curie temperature of iron. The geomagnetic polarity time scale was calibrated largely using K–Ar dating.

Decay series

Further information: Isotopes of potassium

Potassium naturally occurs in 3 isotopes: ³⁹
K
(93.2581%), ⁴⁰
K
(0.0117%), ⁴¹
K
(6.7302%). ³⁹
K
and ⁴¹
K
are stable. The ⁴⁰
K
isotope is radioactive; it decays with a half-life of 1.248×10⁹ years to ⁴⁰
Ca
and ⁴⁰
Ar
. Conversion to stable ⁴⁰
Ca
occurs via electron emission (beta decay) in 89.3% of decay events. Conversion to stable ⁴⁰
Ar
occurs via electron capture in the remaining 10.7% of decay events.

Argon, being a noble gas, is a minor component of most rock samples of geochronological interest: It does not bind with other atoms in a crystal lattice. When ⁴⁰
K
decays to ⁴⁰
Ar
; the atom typically remains trapped within the lattice because it is larger than the spaces between the other atoms in a mineral crystal. But it can escape into the surrounding region when the right conditions are met, such as changes in pressure or temperature. ⁴⁰
Ar
atoms can diffuse through and escape from molten magma because most crystals have melted and the atoms are no longer trapped. Entrained argon – diffused argon that fails to escape from the magma – may again become trapped in crystals when magma cools to become solid rock again. After the recrystallization of magma, more ⁴⁰
K
will decay and ⁴⁰
Ar
will again accumulate, along with the entrained argon atoms, trapped in the mineral crystals. Measurement of the quantity of ⁴⁰
Ar
atoms is used to compute the amount of time that has passed since a rock sample has solidified.

Despite ⁴⁰
Ca
being the favored daughter nuclide, it is rarely useful in dating because calcium is so common in the crust, with ⁴⁰
Ca
being the most abundant isotope. Thus, the amount of calcium originally present is not known and can vary enough to confound measurements of the small increases produced by radioactive decay.

Formula

The ratio of the amount of ⁴⁰
Ar
to that of ⁴⁰
K
is directly related to the time elapsed since the rock was cool enough to trap the Ar by the equation:

$t={\frac {t_{\frac {1}{2}}}{\ln(2)}}\ln \left({\frac {{\ce {K}}_{f}+{\frac {{\ce {Ar}}_{f}}{0.109}}}{{\ce {K}}_{f}}}\right)$,

where:

• t is time elapsed
• t_1/2 is the half-life of ⁴⁰
  K
  
• K_f is the amount of ⁴⁰
  K
  remaining in the sample
• Ar_f is the amount of ⁴⁰
  Ar
  found in the sample.

The scale factor 0.109 corrects for the unmeasured fraction of ⁴⁰
K
which decayed into ⁴⁰
Ca
; the sum of the measured ⁴⁰
K
and the scaled amount of ⁴⁰
Ar
gives the amount of ⁴⁰
K
which was present at the beginning of the elapsed time period. In practice, each of these values may be expressed as a proportion of the total potassium present, as only relative, not absolute, quantities are required.

Obtaining the data

To obtain the content ratio of isotopes ⁴⁰
Ar
to ⁴⁰
K
in a rock or mineral, the amount of Ar is measured by mass spectrometry of the gases released when a rock sample is volatilized in vacuum. The potassium is quantified by flame photometry or atomic absorption spectroscopy.

The amount of ⁴⁰
K
is rarely measured directly. Rather, the more common ³⁹
K
is measured and that quantity is then multiplied by the accepted ratio of ⁴⁰
K
/³⁹
K
(i.e., 0.0117%/93.2581%, see above).

The amount of ⁴⁰
Ar
is also measured to assess how much of the total argon is atmospheric in origin.

Assumptions

According to McDougall & Harrison (1999, p. 11) the following assumptions must be true for computed dates to be accepted as representing the true age of the rock:

• The parent nuclide, ⁴⁰
  K
  , decays at a rate independent of its physical state and is not affected by differences in pressure or temperature. This is a well-founded major assumption, common to all dating methods based on radioactive decay. Although changes in the electron capture partial decay constant for ⁴⁰
  K
  possibly may occur at high pressures, theoretical calculations indicate that for pressures experienced within a body the size of the Earth the effects are negligibly small.
• The ⁴⁰
  K
  /³⁹
  K
  ratio in nature is constant so the ⁴⁰
  K
  is rarely measured directly, but is assumed to be 0.0117% of the total potassium. Unless some other process is active at the time of cooling, this is a very good assumption for terrestrial samples.
• The radiogenic argon measured in a sample was produced by in situ decay of ⁴⁰
  K
  in the interval since the rock crystallized or was recrystallized. Violations of this assumption are not uncommon. Well-known examples of incorporation of extraneous ⁴⁰
  Ar
  include chilled glassy deep-sea basalts that have not completely outgassed preexisting ⁴⁰
  Ar
  *, and the physical contamination of a magma by inclusion of older xenolitic material. The Ar–Ar dating method was developed to measure the presence of extraneous argon.
• Great care is needed to avoid contamination of samples by absorption of nonradiogenic ⁴⁰
  Ar
  from the atmosphere. The equation may be corrected by subtracting from the ⁴⁰
  Ar
  _measured value the amount present in the air where ⁴⁰
  Ar
  is 295.5 times more plentiful than ³⁶
  Ar
  . ⁴⁰
  Ar
  _decayed = ⁴⁰
  Ar
  _measured − 295.5 × ³⁶
  Ar
  _measured.
• The sample must have remained a closed system since the event being dated. Thus, there should have been no loss or gain of ⁴⁰
  K
  or ⁴⁰
  Ar
  *, other than by radioactive decay of ⁴⁰
  K
  . Departures from this assumption are quite common, particularly in areas of complex geological history, but such departures can provide useful information that is of value in elucidating thermal histories. A deficiency of ⁴⁰
  Ar
  in a sample of a known age can indicate a full or partial melt in the thermal history of the area. Reliability in the dating of a geological feature is increased by sampling disparate areas which have been subjected to slightly different thermal histories.

Both flame photometry and mass spectrometry are destructive tests, so particular care is needed to ensure that the aliquots used are truly representative of the sample. Ar–Ar dating is a similar technique that compares isotopic ratios from the same portion of the sample to avoid this problem.

Applications

Due to the long half-life of ⁴⁰
K
, the technique is most applicable for dating minerals and rocks more than 100,000 years old. For shorter timescales, it is unlikely that enough ⁴⁰
Ar
will have had time to accumulate to be accurately measurable. K–Ar dating was instrumental in the development of the geomagnetic polarity time scale. Although it finds the most utility in geological applications, it plays an important role in archaeology. One archeological application has been in bracketing the age of archeological deposits at Olduvai Gorge by dating lava flows above and below the deposits. It has also been indispensable in other early east African sites with a history of volcanic activity such as Hadar, Ethiopia. The K–Ar method continues to have utility in dating clay mineral diagenesis. In 2017, the successful dating of illite formed by weathering was reported. This finding indirectly led to the dating of the strandflat of Western Norway from where the illite was sampled. Clay minerals are less than 2 μm thick and cannot easily be irradiated for Ar–Ar analysis because Ar recoils from the crystal lattice.

In 2013, the K–Ar method was used by the Mars Curiosity rover to date a rock on the Martian surface, the first time a rock has been dated from its mineral ingredients while situated on another planet.

References

• Aronson, J. L.; Lee, M. (1986). "K/Ar systematics of bentonite and shale in a contact metamorphic zone". Clays and Clay Minerals. 34 (4): 483–487. Bibcode:1986CCM....34..483A. doi:10.1346/CCMN.1986.0340415.
• McDougall, I.; Harrison, T. M. (1999). Geochronology and thermochronology by the ⁴⁰Ar/³⁹Ar method. Oxford University Press. ISBN 978-0-19-510920-7.
• Tattersall, I. (1995). The Fossil Trail: How We Know What We Think We Know About Human Evolution. Oxford University Press. ISBN 978-0-19-506101-7.

Further reading

• "K/Ar and ⁴⁰K/³⁹K methodology". New Mexico Geochronology Research Laboratory. Archived from the original on 17 April 2006.
• Michaels, G. H.; Fagan, B. M. (15 December 2005). "Chronological Methods 9: Potassium-Argon Dating". University of California. Archived from the original on 10 August 2010.
• Moran, T. J. (2009). "Teaching Radioisotope Dating Using the Geology of the Hawaiian Islands" (PDF). Journal of Geoscience Education. 57 (2): 101–105. Bibcode:2009JGeEd..57..101M. doi:10.5408/1.3544237.