# Electron spin resonance dating

Electron Spin Resonance Dating, or ESR dating, is a technique used to date newly formed materials, which Radiocarbon dating cannot, like carbonates, tooth enamel, or materials that have been previously heated like igneous rock. Electron spin resonance dating was first introduced to the science community in 1975, when Motoji Ikeya dated a speleothem in Akiyoshi Cave, Japan.[1] ESR dating measures the amount of unpaired electrons in crystalline structures that were previously exposed to natural radiation. The age of substance can be determined by measuring the dosage of radiation since the time of its formation.[2]

## Applications

Electron Spin Resonance Dating is being used in fields like radiation chemistry, biochemistry, and as well as geology, archaeology, and anthropology.[3] ESR dating is used instead of Radiocarbon dating because ESR dating can date newly formed materials or previously heated rock.[4] The dating of buried teeth has served as the basis for the dating of human remains.[1] Studies have been used to date burnt flint and quartz found in certain ancient ceramics.[5] Newer ESR dating applications include dating previous earthquakes from fault gouge, past volcanic eruptions, and tectonic activity along coastlines.[4]

## Dating Process

Electron spin resonance dating can be described as trapped charge dating. Radioactivity causes negatively charged electrons to move from a ground state, the valence band, to a higher energy level at the conduction band. After a short time, electrons eventually recombine with the positively charged holes left in the valence band.[5] The trapped electrons form para-magnetic centers and give rise to certain signals that can be detected under an ESR spectrometry.[1] The amount of trapped electrons corresponds to the magnitude of the ESR signal. This ESR signal is directly proportional to the number of trapped electrons in the mineral, the dosage of radioactive substances, and the age.[1]

### Calculating the ESR Age

The electron spin resonance age of a substance is found from the following equation:

${\displaystyle D_{E}=\int _{0}^{T}D(t).dt}$

where DE is the equivalent dose, or paleodose (in Gray or Gy), i.e. the amount of radiation a sample has received during the time elapsed between the zeroing of the ESR clock (t = 0) and the sampling (t = T). D(t) is the dose rate (usually in Gy/ka or microGy/a), which is the average dose absorbed by the sample in 1 year. If D(t) is considered constant over time, then, the equation may be expressed as follows:

${\displaystyle T=D_{E}/D}$[1]

In this scenario, T is the age of the sample, i.e. the time during which the sample has been exposed to natural radioactivity since the ESR signal has been last reset. This happens by releasing the trapped charge, i.e. usually by either dissolution/recrystallization, heat, optical bleaching, or mechanical stress.[6]

#### Determining the Accumulated Dose

The accumulated dose is found by the additive dose method[2] and by an electron spin resonance (ESR) spectrometry.[1] This when a sample is put into an external magnetic field and irradiated with certain dosages of microwaves[1] that changes the energy level of the magnetic centers (changes the spin rotation) either to the same or opposite of the surrounding magnetic field.[3] The change in magnetic properties only happens at specific energy levels and for certain microwave frequencies, there are specific magnetic strengths that cause these changes to occur (resonance).[1] Positioning an ESR line in a spectrum corresponds to the proportion (g-value) of the microwave frequency to magnetic field strength used in the spectrometry.[1] As the extrapolation toward zero of the ESR intensity occurs, the accumulated dose can then be determined.[2]

#### Determining the Dose Rate

The dose rate is found from the summation of the concentrations of radioactive materials in the sample (internal dose rate) and its surrounding environment (external dose rate). The dosages of internal and external radioactivity must be calculated separately because of the varying differences between the two.[1]

Factors to include in calculating the radioactivity:

• Uranium, Thorium and Potassium concentration[2]
• Energies for alpha, beta and gamma rays of Uranium-238 and Thorium-232[3]
• Correction factors related to the water content, the geometry of the sample, its thickness and density
• Cosmic ray dose rates – dependent on geographical position and thickness of covering sediments (300 pGy/a at sea level)[1]

## Reliability

Trapped electrons only have a limited time frame when they are within the intermediate energy level stages. After a certain time range, or temperature fluctuations, trapped electrons will return to their energy states and recombine with holes.[1] The recombination of electrons with their holes is only negligible if the average life is ten times higher than the age of the sample being dated.[1]

## References

1. Grun, Rainer (1991). "ELECTRON SPIN RESONANCE DATING AND THE EVOLUTION OF MODERN HUMANS" (PDF). in-africa.org. Retrieved 2015-10-20.
2. ^ a b c d Radtke, Ulrich; Grün, Rainer; Schwarcz, Henry P. (1988). "Electron spin resonance dating of the Pleistocene coral reef tracts of Barbados". Quaternary Research. 29 (3): 197–215. Bibcode:1988QuRes..29..197R. doi:10.1016/0033-5894(88)90030-0. Retrieved 2015-10-20.
3. ^ a b c Ikeya, M. (1993-01-01). New Applications of Electron Spin Resonance: Dating, Dosimetry and Microscopy. World Scientific. ISBN 9789810212001.
4. ^ a b Rink, W. J (1997-12-05). "Electron spin resonance (ESR) dating and ESR applications in quaternary science and archaeometry". Radiation Measurements. 27 (5–6): 975–1025. Bibcode:1997RadM...27..975R. doi:10.1016/S1350-4487(97)00219-9.
5. ^ a b Grün, Rainer (1997-01-01). "Electron Spin Resonance Dating". In Taylor, R. E.; Aitken, Martin J. (eds.). Chronometric Dating in Archaeology. Advances in Archaeological and Museum Science. Springer US. pp. 217–260. doi:10.1007/978-1-4757-9694-0_8. ISBN 978-1-4757-9696-4.
6. ^ Ikeya, Motoji (1993). New Applications of Electron Spin Resonance. World Scientific. ISBN 978-981-4317-21-4.