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  • 19.01.2019
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Electron Spin Resonance Dating . SpringerLink

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Electron paramagnetic resonance EPR spectroscopy is a powerful and versatile technique that is frequently used for quantitative and qualitative analysis in a wide range of scientific fields such as chemistry , physics, biology, medicine, geology and archaeology. It can be especially useful for the characterisation of matter, providing information about the nature of the paramagnetic species present, as well as the structure of their local environment. This numerical dating method is based on the study of the radioactive decay of 14 C in organisms after their death and may provide accurate ages for samples containing organic matter like fossil bones or charcoals. Radiocarbon is usually classified as a radiometric dating method, which corresponds to a group of techniques based on the measurement of the radioactive decay or production of specific radioelements e. But there is also another group of dating approaches that are based instead on the evaluation of the effects of natural radioactivity on some materials over time, which are quantified in terms of the radiation dose absorbed i. These are usually called palaeodosimetric or trapped charge dating methods, mainly based either on the study of radiation-induced luminescence, e. The first application of EPR for a dating purpose was carried out during the mids on a stalagmite from a Japanese cave, 1 about 30 years after the discovery of EPR by E.

In this case, the maximum sediment thickness above the sample should be estimated as well. Nevertheless, as far as possible, the gamma dose rate should always be derived from in situ measurements. Sometimes, fossil teeth are taken from collections and their exact original location spot may no longer exist. Consequently, in situ measurements have to be performed as closely as possible to the tooth original position.

Indeed, a tooth cannot be dated without a good knowledge of its sedimentary context, since the dose rate needs to be accurately reconstructed. By definition, field work is the first step of the ESR dating procedure, and the reliability of the age result depends on the accuracy of the data collected on site, such as the position of the tooth and its embedding sediment, the in situ dosimetry measurements and the estimation of the thickness of the overlying deposits.

In order to implement ESR dating under the best possible conditions, we provided here some guidelines and designed a sampling form for non-ESR specialists intending to sample teeth, as it includes all the data necessary to record and report for an ESR age calculation.

The tooth and sediment sampling can be easily performed by following the basic instructions given above and should be carried out while the excavation is still ongoing. However, the involvement of an ESR specialist in the field is highly recommended, in particular for in situ dosimetry matter.

ESR -Electron Spin Resonance- - principle, working & application

Quaternary International1 World Scientific Publishing, Singapour, p. Archea, Tours, p. In Rink W. EdsEncyclopedia of Scientific Dating Methods. Springer Netherlands, Quaternary Geochronology6 5 Ancient TL25 1 Radiation Measurements23 Quaternary Geochronology 30 part B PACT6 Email: mailys.

tablished and common dating techniques such as uranium series (U-series) or ar - gon-argon to obtain electron spin resonance (ESR) age estimates. D. Apers, R. Debuyst, P. DeCanniere, F. Dejehet, E. LombardA criticism of the dating by electron paramagnetic resonance (ESR) of the stalagmitic floors of the . Science. Feb 29;() Electron spin resonance dating of animal and human bones. Ikeya M, Miki T. Ages of fossil bones were determined by.

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Mathieu Duval raises the question “Dating fossil teeth by electron paramagnetic resonance: how is that possible?”. Whilst we are all familiar. Electron spin resonance (ESR) dating was introduced into archaeology about 20 years ago. ESR dating in archaeology has been applied to tooth enamel, speleothems, spring deposited travertines, shells and burnt flint. These applications are described in detail and examples are given. ESR dating determines how long a sample has been exposed to the radiation level of its Electron paramagnetic resonance allows.

Plan 1 - Introduction. If these species are lacking from the faunal assemblage, smaller teeth, from species such as cervid and ovicaprid, can be collected, whereas carnivora teeth are usually not recommended, given their thin enamel layer; 8 — the selected tooth should preferentially be well preserved, as previous studies show a direct correlation between fractures and diagenetic weaknesses in dental tissues and preferential migration of U-series elements e.

This would indeed precludes an accurate reconstruction of the dose rate, as it is by definition based on the data collected from the present-day conditions; 10 — if possible, the sample must be collected with its embedding sediment, from which U, Th and K contents will be measured in order to evaluate the beta dose rate received by the tooth. Agrandir Originalk.

Table des illustrations Titre Fig. The objective of this article is to explain how EPR may be converted into a dating tool for fossil teeth. By definition, EPR spectroscopy is a technique designed for the study of paramagnetic species, i. These may be either naturally present in some materials, or created by physical or chemical reactions.

With regard to the latter, some materials can acquire paramagnetic properties under the effect of radioactivity. The interaction of ionising radiations with the matter may induce modifications of the electronic structure of some materials: electric charges electrons or holes may be trapped in the crystalline network, thereby forming radiation-nduced paramagnetic species. These species create a signal that can be detected by EPR spectroscopy, the intensity of which is directly dependent on the amount of trapped charges in the crystalline network, reflecting thus the dose absorbed by the material.

EPR spectroscopy is now widely recognised as a reference technique for routine dosimetry by many international institutions [e. Over the last decades, many applications have been developed, including those for post-accident dose reconstruction in the environment, biophysical dosimetry using human tissues, to identify irradiated foods, and some of them, such as the alanine dosimetry, have reached a high-level of standardisation.

Dosimetric properties of tooth enamel have been known for more than 40 years.

Electron Spin Resonance Dating

Hydroxyapatite, the main component of bones and teeth, is especially sensitive to ionising radiation: this material is able naturally to register doses from only a few mGy to several thousand of Gy. It is now internationally accepted as a valuable natural EPR dosimeter, and is commonly used in the field of retrospective dosimetry for persons accidentally exposed to ionising radiation. An extensive review on this aspect may be found in Reference 4.

From a mineralogical point of view, tooth enamel is mainly made of carbonated hydroxyapatite [Ca 10 PO 4 6 OH 2 ] like dentine or bones. These characteristics make tooth enamel especially stable over time, i. The EPR signal associated with fossil hydroxyapatite is an asymmetric composite signal.

The main radiation-induced signal is defined by three peaks T1, B1 and B2, see Figure 1. Many contributions to this signal have been identified, mainly carbonate-derived radicals and some oxygen radicals, 4 but the major contribution comes from three kinds of CO 2 — radicals, whose precursors are very likely the carbonate groups CO 3 2— present in the hydroxyapatite.

Once an animal is dead, its teeth become progressively buried by sediment during the geological periods, during which the enamel is naturally exposed to ionising radiations from cosmic rays and from the radioactivity of the sediment and the tooth itself.

This natural radioactivity is due to the radioelements, mainly U-series, Th-series and 40 K elementsthat are not only naturally present in the sediment, but are also progressively incorporated into the dental tissues.

Dating fossil teeth by electron paramagnetic resonance: how is that possible?

Ionising radiations emitted by these radioelements are alpha and beta particles as well as gamma rays Figure 1. Together with cosmic rays, they contribute to build up a dose in the enamel over time, the magnitude of which will mainly depend on two main parameters: the duration of the exposure to radioactivity, and the strength of this radioactivity.

This relationship may be converted into an EPR age equation as follows:. This work is carried out in two different ways: the D E is obtained by using EPR spectroscopy, while D t is derived from the evaluation of the strength of the radioactivity present in the sample and its surrounding environment.

To obtain an accurate evaluation of the total dose rate, it is important to divide it into several components. The specificity of teeth dating relies on the complex system that has to be considered, because a tooth is usually made by several tissues enamel, dentine and, sometimes, cement; Figure 2having various thicknesses and composition.

The geometry of the enamel and its surrounding thus has to be considered in the dose rate reconstruction. In the case of a tooth with an enamel layer surrounded by cement and dentine, the dose rate equation may be expressed as follows:.

Dating electron spin

Consequently, with this specific configuration, the internal dose rate within the enamel comes from alpha and beta particles, while the surrounding tissues only provide an external beta contribution. The gamma rays contribution only comes from the sediment, since the absorption by the enamel of the gamma rays coming from the enamel itself and the other tissues can be neglected.

In the case of a tooth with an enamel layer in direct contact with the sediment on the outer side i. Dental tissues are usually assumed to be free of Th and 40 K, since their incorporation into the crystalline network is very complicated, owing to their mobility and atomic radius, respectively.

Consequently, the dose rate components associated to dental tissues are directly, and only, dependent on the uranium concentration. However, dental tissues behave as open systems for U, i. It is therefore crucial not only to measure the actual U-content but also to know its evolution in the past. Indeed, one may intuitively understand that the total dose absorbed by the enamel will be somewhat different if the uranium was accumulated in the dental tissues shortly after the death of the animal or if it happened only very recently.

The US model defined by these authors is based on the following equation:. Examples of dating applications may be found in Reference 9. An EPR age estimate is the result of a long analytical process, made by five main steps associating fieldwork and laboratory procedures: i sampling and in situ measurements, ii sample preparation, iii EPR dosimetry, iv evaluation of the natural radioactivity of the sample itself and its surrounding environment, and v EPR age calculation.

Fossil teeth are usually collected either on site or chosen from collections.

Large mammal teeth, and especially from herbivores, are usually preferred, since they offer a thicker enamel layer. Then, in situ measurements of the natural radioactivity at the exact place where the sample was collected during excavations, or at least the closest possible, is carried out to evaluate the gamma dose rate.

Philos Trans R Soc Lond B Biol Sci. Aug 29;() Electron spin resonance (ESR) dating of the origin of modern man. Schwarcz HP(1), Grun R. 3Electron Spin Resonance can be used to date fossil teeth with an age ranging from around 2 Ma to 30 ka (for details see for example Grun, ; Ikeya, ). Electron Spin Resonance Dating, or ESR dating, is a technique used to date newly formed materials, which Radiocarbon dating cannot, like carbonates, tooth .

Classically, various techniques may be employed: synthetic TL dosimeters e. In the laboratory, the fossil tooth is prepared by separating mechanically each dental tissue.

The enamel layer is then cleaned, usually with a dentist drill, and gently powdered, in order to avoid significant angular dependence of the EPR signal within the resonator and to improve sample homogeneity. This is why EPR must be considered as a destructive dating method. Each aliquot is then measured at room temperature by EPR spectrometry in order to study the behaviour of the EPR signal with the increasing dose values see Figure 1. Routine quantitative measurements are usually performed by X-band EPR spectrometry, since it offers a good compromise between sensitivity and measurement repeatability in comparison with higher frequency bands.

The experimental setup for quantitative EPR measurements is specifically designed to ensure the stability of the system, including air conditioning and chiller to control the temperature of the water circulating in the magnet. Measurements are thus performed under controlled experimental conditions and following a standardised analytical protocol, in order to minimise any sources of uncertainty that could affect the repeatability of the measurements see further details in Duval et al.

EPR intensities are then extracted from each spectrum, usually by peak-to-peak measurements between T1 and B2 Figure 1 and plotted vs the irradiation doses in order to obtain a growth curve or dose response curve.

A given function, usually a single saturating exponential or a double saturating exponential function, is fitted through the EPR experimental data points. By definition, this function is supposed to describe the behaviour of the radiation-induced EPR signal of tooth enamel since the death of the animal i. If the gamma dose rate is assessed in situthe beta dose rate from the sediment if it applies should preferably be assessed in the laboratory from the sediment sample that was collected around the tooth.

Various laboratory analytical techniques may be used to calculate the radioelement contents of the sediment, e. Other techniques, like beta counting for example, may directly provide a total beta or gamma dose rate value. To do so, mass spectrometry techniques are now usually employed [e.

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