Figure 1: The three stages of thermoluminescence as outlined by Aitken (1985, 1998) and applied to a quartz grain (Keizars, 2008b)Figure 2: The process of recharging and discharging thermoluminescent signal, as applied to beach sands. (modified from Aitken, 1998; Keizars, 2008a)Figure 3: Thermoluminescence signature lost during migration of two sand grain sizes (Keizars, 2008).Figure 4: Illustrated method of passively monitoring sand input (Keizars, 2003).
Thermoluminescence dating (TL) is the determination, by means of measuring the accumulated radiation dose, of the time elapsed since material containing crystalline minerals was either heated (lava, ceramics) or exposed to sunlight (sediments). As a crystalline material is heated during measurements, the process of thermoluminescence starts. Thermoluminescence emits a weak light signal that is proportional to the radiation dose absorbed by the material. It is a type of luminescence dating.
The technique has wide application, and is relatively cheap at some US$300–700 per object; ideally a number of samples are tested. Sediments are more expensive to date.[1] The destruction of a relatively significant amount of sample material is necessary, which can be a limitation in the case of artworks. The heating must have taken the object above 500°C, which covers most ceramics, although very high-fired porcelain creates other difficulties. It will often work well with stones that have been heated by fire. The clay core of bronze sculptures made by lost wax casting is also able to be tested.[2]
Different materials vary considerably in their suitability for the technique, depending on several factors. Subsequent irradiation, for example if an x-ray is taken, can affect accuracy, as will the "annual dose" of radiation a buried object has received from the surrounding soil. Ideally this is assessed by measurements made at the precise findspot over a long period. For artworks, it may be sufficient to confirm whether a piece is broadly ancient or modern (that is, authentic or a fake), and this may be possible even if a precise date cannot be estimated.[2]
Functionality
Natural crystalline materials contain imperfections: impurity ions, stress dislocations, and other phenomena that disturb the regularity of the electric field that holds the atoms in the crystalline lattice together. These imperfections lead to local humps and dips in the crystalline material's electric potential. Where there is a dip (a so-called "electron trap"), a free electron may be attracted and trapped.
The flux of ionizing radiation—both from cosmic radiation and from natural radioactivity—excites electrons from atoms in the crystal lattice into the conduction band where they can move freely. Most excited electrons will soon recombine with lattice ions, but some will be trapped, storing part of the energy of the radiation in the form of trapped electric charge (Figure 1).
Depending on the depth of the traps (the energy required to free an electron from them) the storage time of trapped electrons will vary as some traps are sufficiently deep to store charge for hundreds of thousands of years.
In practical use
Another important technique in testing samples from a historic or archaeological site is a process known as thermoluminescence testing, which involves the principle that all objects absorb radiation from the environment. This process frees electrons within elements or minerals that remain caught within the item. Thermoluminescence testing involves heating a sample until it releases a type of light, which is then measured to determine the last time the item was heated.
In thermoluminescence dating, these long-term traps are used to determine the age of materials: When irradiated crystalline material is again heated or exposed to strong light, the trapped electrons are given sufficient energy to escape. In the process of recombining with a lattice ion, they lose energy and emit photons (light quanta), detectable in the laboratory.
The amount of light produced is proportional to the number of trapped electrons that have been freed which is in turn proportional to the radiation dose accumulated. In order to relate the signal (the thermoluminescence—light produced when the material is heated) to the radiation dose that caused it, it is necessary to calibrate the material with known doses of radiation since the density of traps is highly variable.
Thermoluminescence dating presupposes a "zeroing" event in the history of the material, either heating (in the case of pottery or lava) or exposure to sunlight (in the case of sediments), that removes the pre-existing trapped electrons. Therefore, at that point the thermoluminescence signal is zero.
As time goes on, the ionizing radiation field around the material causes the trapped electrons to accumulate (Figure 2). In the laboratory, the accumulated radiation dose can be measured, but this by itself is insufficient to determine the time since the zeroing event.
The Radiation Dose Rate - the dose accumulated per year-must be determined first. This is commonly done by measurement of the alpha radioactivity (the uranium and thorium content) and the potassium content (K-40 is a beta and gamma emitter) of the sample material.
Often the gamma radiation field at the position of the sample material is measured, or it may be calculated from the alpha radioactivity and potassium content of the sample environment, and the cosmic ray dose is added in. Once all components of the radiation field are determined, the accumulated dose from the thermoluminescence measurements is divided by the dose accumulating each year, to obtain the years since the zeroing event.
Relation to radiocarbon dating
Thermoluminescence dating is used for material where radiocarbon dating is not available, like sediments. Its use is now common in the authentication of old ceramic wares, for which it gives the approximate date of the last firing. An example of this can be seen in Rink and Bartoll, 2005.
Thermoluminescence dating was modified for use as a passive sand migration analysis tool by Keizars, et al., 2008 (Figure 3), demonstrating the direct consequences resulting from the improper replenishment of starving beaches using fine sands, as well as providing a passive method of policing sand replenishment and observing riverine or other sand inputs along shorelines (Figure 4).
Typical quartz TL curve measured with a UV filter during routine TL dating.
Oxford Authentication: Home - TL Testing Authentication 'Oxford Authentication® Ltd authenticates ceramic antiquities using the scientific technique of thermoluminescence (TL). TL testing is a dating method for archaeological items which can distinguish between genuine and fake antiquities.' See some of their case studies here: https://www.oxfordauthentication.com/case-studies/
References and bibliography
GlobalNet.co.uk, Quaternary TL Surveys - Guide to thermoluminescence date measurement
Aitken, M.J., Thermoluminescence Dating, Academic Press, London (1985) – Standard text for introduction to the field. Quite complete and rather technical, but well written and well organized. There is a second edition.
Aitken, M.J., Introduction to Optical Dating, Oxford University Press (1998) – Good introduction to the field.
Keizars, K.Z. 2003. NRTL as a method of analysis of sand transport along the coast of the St. Joseph Peninsula, Florida. GAC/MAC 2003. Presentation: Brock University, St. Catharines, Ontario, Canada.
JCRonline.org, Ķeizars, Z., Forrest, B., Rink, W.J. 2008. Natural Residual Thermoluminescence as a Method of Analysis of Sand Transport along the Coast of the St. Joseph Peninsula, Florida. Journal of Coastal Research, 24: 500–507.
Keizars, Z. 2008b. NRTL trends observed in the sands of St. Joseph Peninsula, Florida. Queen's University. Presentation: Queen's University, Kingston, Ontario, Canada.
Liritzis, I., 2011. Surface Dating by Luminescence: An Overview. Geochronometria, 38(3): 292–302.
Mortlock, AJ; Price, D and Gardiner, G. The Discovery and Preliminary Thermoluminescence Dating of Two Aboriginal Cave Shelters in the Selwyn Ranges, Queensland [online]. Australian Archaeology, No. 9, Nov 1979: 82–86. Availability: <> ISSN0312-2417. [cited 04 Feb 15].
Antiquity.ac.uk, Rink, W. J., Bartoll, J. 2005. Dating the geometric Nasca lines in the Peruvian desert. Antiquity, 79: 390–401.
Sullasi, H. S., Andrade, M. B., Ayta, W. E. F., Frade, M., Sastry, M. D., & Watanabe, S. (2004). Irradiation for dating Brazilian fish fossil by thermoluminescence and EPR technique. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 213, 756–760.doi:10.1016/S0168-583X(03)01698-7[permanent dead link]
Radiometric dating, radioactive dating or radioisotope dating is a technique which is used to date materials such as rocks or carbon, in which trace radioactive impurities were selectively incorporated when they were formed. The method compares the abundance of a naturally occurring radioactive isotope within the material to the abundance of its decay products, which form at a known constant rate of decay. The use of radiometric dating was first published in 1907 by Bertram Boltwood and is now the principal source of information about the absolute age of rocks and other geological features, including the age of fossilized life forms or the age of Earth itself, and can also be used to date a wide range of natural and man-made materials.
A radiation dosimeter is a device that measures dose uptake of external ionizing radiation. It is worn by the person being monitored when used as a personal dosimeter, and is a record of the radiation dose received. Modern electronic personal dosimeters can give a continuous readout of cumulative dose and current dose rate, and can warn the wearer with an audible alarm when a specified dose rate or a cumulative dose is exceeded. Other dosimeters, such as thermoluminescent or film types, require processing after use to reveal the cumulative dose received, and cannot give a current indication of dose while being worn.
Luminescence is the "spontaneous emission of radiation from an electronically excited species not in thermal equilibrium with its environment", according to the IUPAC definition. A luminescent object is emitting "cold light", in contrast to "incandescence", where an object only emits light after heating. Generally, the emission of light is due to the movement of electrons between different energy levels within an atom after excitation by external factors. However, the exact mechanism of light emission in "vibrationally excited species" is unknown, as seen in sonoluminescence.
Photoluminescence is light emission from any form of matter after the absorption of photons. It is one of many forms of luminescence and is initiated by photoexcitation, hence the prefix photo-. Following excitation, various relaxation processes typically occur in which other photons are re-radiated. Time periods between absorption and emission may vary: ranging from short femtosecond-regime for emission involving free-carrier plasma in inorganic semiconductors up to milliseconds for phosphoresence processes in molecular systems; and under special circumstances delay of emission may even span to minutes or hours.
Cathodoluminescence is an optical and electromagnetic phenomenon in which electrons impacting on a luminescent material such as a phosphor, cause the emission of photons which may have wavelengths in the visible spectrum. A familiar example is the generation of light by an electron beam scanning the phosphor-coated inner surface of the screen of a television that uses a cathode ray tube. Cathodoluminescence is the inverse of the photoelectric effect, in which electron emission is induced by irradiation with photons.
Geochronology is the science of determining the age of rocks, fossils, and sediments using signatures inherent in the rocks themselves. Absolute geochronology can be accomplished through radioactive isotopes, whereas relative geochronology is provided by tools such as paleomagnetism and stable isotope ratios. By combining multiple geochronological indicators the precision of the recovered age can be improved.
Phosphorescence is a type of photoluminescence related to fluorescence. When exposed to light (radiation) of a shorter wavelength, a phosphorescent substance will glow, absorbing the light and reemitting it at a longer wavelength. Unlike fluorescence, a phosphorescent material does not immediately reemit the radiation it absorbs. Instead, a phosphorescent material absorbs some of the radiation energy and reemits it for a much longer time after the radiation source is removed.
In physics, optically stimulated luminescence (OSL) is a method for measuring doses from ionizing radiation. It is used in at least two applications:
Thermoluminescence is a form of luminescence that is exhibited by certain crystalline materials, such as some minerals, when previously absorbed energy from electromagnetic radiation or other ionizing radiation is re-emitted as light upon heating of the material. The phenomenon is distinct from that of black-body radiation.
An F center or Farbe center is a type of crystallographic defect in which an anionic vacancy in a crystal lattice is occupied by one or more unpaired electrons. Electrons in such a vacancy in a crystal lattice tend to absorb light in the visible spectrum such that a material that is usually transparent becomes colored. The greater the number of F centers, the more intense the color of the compound. F centers are a type of color center.
A diamond anvil cell (DAC) is a high-pressure device used in geology, engineering, and materials science experiments. It enables the compression of a small (sub-millimeter-sized) piece of material to extreme pressures, typically up to around 100–200 gigapascals, although it is possible to achieve pressures up to 770 gigapascals.
Radiochemistry is the chemistry of radioactive materials, where radioactive isotopes of elements are used to study the properties and chemical reactions of non-radioactive isotopes. Much of radiochemistry deals with the use of radioactivity to study ordinary chemical reactions. This is very different from radiation chemistry where the radiation levels are kept too low to influence the chemistry.
Radioluminescence is the phenomenon by which light is produced in a material by bombardment with ionizing radiation such as alpha particles, beta particles, or gamma rays. Radioluminescence is used as a low level light source for night illumination of instruments or signage. Radioluminescent paint is occasionally used for clock hands and instrument dials, enabling them to be read in the dark. Radioluminescence is also sometimes seen around high-power radiation sources, such as nuclear reactors and radioisotopes.
Absolute dating is the process of determining an age on a specified chronology in archaeology and geology. Some scientists prefer the terms chronometric or calendar dating, as use of the word "absolute" implies an unwarranted certainty of accuracy. Absolute dating provides a numerical age or range, in contrast with relative dating, which places events in order without any measure of the age between events.
Luminescence dating refers to a group of chronological dating methods of determining how long ago mineral grains were last exposed to sunlight or sufficient heating. It is useful to geologists and archaeologists who want to know when such an event occurred. It uses various methods to stimulate and measure luminescence.
A thermoluminescent dosimeter, or TLD, is a type of radiation dosimeter, consisting of a piece of a thermoluminescent crystalline material inside a radiolucent package.
Promethium(III) chloride is a chemical compound of promethium and chlorine with the formula PmCl3. It is an ionic, water soluble, crystalline salt that glows in the dark with a pale blue or green light due to promethium's intense radioactivity.
Electron spin resonance dating, or ESR dating, is a technique used to date materials which radiocarbon dating cannot, including minerals, biological materials, archaeological materials and food. Electron spin resonance dating was first introduced to the science community in 1975, when Japanese nuclear physicist Motoji Ikeya dated a speleothem in Akiyoshi Cave, Japan. ESR dating measures the amount of unpaired electrons in crystalline structures that were previously exposed to natural radiation. The age of a substance can be determined by measuring the dosage of radiation since the time of its formation.
The Philippine Nuclear Research Institute (PNRI) is a government agency under the Department of Science and Technology mandated to undertake research and development activities in the peaceful uses of nuclear energy, institute regulations on the said uses, and carry out the enforcement of said regulations to protect the health and safety of radiation workers and the general public.
Optically stimulated luminescence (OSL) thermochronometry is a dating method used to determine the time since quartz and/or feldspar began to store charge as it cools through the effective closure temperature. The closure temperature for quartz and Na-rich K-feldspar is 30-35 °C and 25 °C respectively. When quartz and feldspar are beneath the earth, they are hot. They cool when any geological process e.g. focused erosion causes their exhumation to the earth surface. As they cool, they trap electron charges originating from within the crystal lattice. These charges are accommodated within crystallographic defects or vacancies in their crystal lattices as the mineral cools below the closure temperature.
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