Luminescence dating: laboratory procedures and protocols

In the last 30 years, from 1967 to 1997, the use of luminescence signals from naturally occurring minerals has gone though a major metamorphosis, from thermoluminescence (TL) dating of pottery to optically stimulated luminescence (OSL) dating of sediments. Laboratory procedures for dating sediments have been adapted from those for pottery and new procedures have been developed as the need arises.

The majority of sediment dating applications are carried out on quartz and potassium-rich feldspars and the general characteristics of the TL and OSL signals from these minerals are reviewed. For sediments some new problems were encountered, with some grains perhaps not being completely bleached at deposition. For OSL signals there is no simple procedure for the selection of a thermally stable signal, as there had been in the case of pottery.

Many different laboratory protocols have been developed as our understanding of the fundamental behaviour of luminescence signals from quartz and feldspar has improved. These protocols are explained and discussed, giving the advantages and disadvantages of each procedure as applied to different types of sediment.

This review is presented as a guide to the selection of the most appropriate procedure for a particular dating application.     

Luminescence spectra of alkalifeldspars and plagioclases

Feldspars are widely used as dosimeters in dating archaeological and geological materials by thermally or optically stimulated luminescence (TL, OSL). The TL, (IR)OSL and phosphorescence (following gamma irradiation) spectra of 26 samples covering the orthoclase-albite-anorthite ternary system, which were characterized by microscopy and X-ray diffraction analysis, were measured using the Freiberg high sensitive luminescence spectrometer. The range of observation for TL (up to 350°C) and phosphorescence was (200–800) nm. IR (880 nm) stimulated luminescence light has been detected between 330 nm and 660 nm. Representative examples of our systematic investigations on the luminescence behaviour of alkalifeldspars and plagioclases are presented.     

Mechanisms of luminescent responses in thermal and optical stimulation of potassium feldspars

We propose a model describing the mechanism for generation of an optically stimulated luminescence signal in potassium feldspars when irradiated in an IR absorption band (IR OSL). The model assumes that this type of stimulated luminescence is intercenter by nature, arising in tightly bound deep trap/ionized luminescence center pairs. At the same time, the thermoluminescence (TL) signal and the optically stimulated afterglow (OSA) signal arise in a recombination process with participation of the conduction band. We describe the results of an experimental test of the proposed model.     

OSL properties of NaCl relative to dating and dosimetry

The luminescence properties of NaCl are discussed. Attention is focussed predominantly upon the optically stimulated luminescence (OSL) signal (UV emission) of NaCl (420–560 nm stimulation). The results from experiments relevant to geological dating applications, such as signal resetting, dose response and thermal stability, are described. The behaviour of the OSL signal observed was found to be favourable for dating, with both the thermal stability and dose response suggesting a range of at least 10 ka. Signal resetting via optical exposure was found to be extremely rapid and no evidence of either thermoluminescence or OSL signals was found following re-crystallization. The potential for dating natural salt deposits, as found in various arid environments, appears to be good.     

The timing of OSL sensitivity changes in a natural quartz

The timing of 110°C thermoluminescence (TL) and optically stimulated luminescence (OSL) sensitivity changes is explored using a natural (aeolian) quartz sample from Australia that was previously found to exhibit marked dose-dependent sensitivity change. The changes occur asynchronously; the 110°C TL sensitivity changes after dosing plus pre-heating, whereas the OSL sensitivity changes (proportionately with dose) after optical bleaching. Although the magnitude and saturation characteristics of the sensitivity changes are found to be similar, their non-synchronicity negates a direct link between the phenomena. Implications of these results for dating procedures are discussed. In particular, the results indicate that a single aliquot additive dose procedure similar to that developed for coarse-grained potassium feldspar should be possible for some quartz samples.     

Investigating the thermally transferred optically stimulated luminescence source trap in fired geological quartz

The pre-dosed thermoluminescence (TL) emission of quartz has been found to be useful in retrospective dosimetry and archaeometry. Though the pre-dosed optically stimulated luminescence (OSL) and TL emissions have been reported to be similar, the former has been found to be un-reliable for the equivalent dose estimation. As this measurement protocol involves thermal heating at around 400 °C, the work reported in this paper investigated the influence of this heating on the OSL using fired specimens from various regions. The results suggested that the discrepancy in the behaviour of two emissions is caused by the presence of the thermally transferred optically stimulated luminescence (TT-OSL) induced by thermal-activation involved in the pre-dose treatment. This transferred signal was observed to be very significant in the case of samples containing a prominent higher-temperature TL peak at ∼375 °C. The characterization of this signal based on (i) the nature of the glow curves, (ii) thermal-annealing of the OSL trap, (iii) observation of the TT-OSL, (iv) bleaching of the source trap and (v) the correlation between TL and OSL seems to suggest that the trap corresponding to this TL peak is the source trap in the TT-OSL emission mechanism.     

Study of sensitivity change of OSL signals from quartz and feldspars as a function of preheat temperature

Optically stimulated luminescence (OSL) signals from feldspar and quartz samples were studied using infrared (860 nm) and green light (420–575 nm) stimulation. A serious problem connected with the regeneration technique used for dating is associated with a change of OSL sensitivity to radiation in the course of the measurement process. A typical effect seen is a large increase of the apparent strength of our beta source when calibrated against a gamma source. If the regeneration procedure is used, it is shown that the sensitivity increases up to 50% during the measurement process and as a result, the equivalent dose (ED) would be underestimated. A study of sensitivity changes in feldspars and quartz was carried out with emphasis on the effect of preheat and annealing on the OSL signal. Measurement results obtained are presented, and possible elimination of errors in dating caused by sensitivity changes is discussed.     

Further investigations of tunneling recombination processes in random distributions of defects

The shape of infrared stimulated luminescence signals (IRSL) from feldspars has been the subject of numerous studies in the field of luminescence dating. Specifically linearly modulated IRSL signals (LM-IRSL) are commonly assumed to consist of several first order components corresponding to distinct optical stimulation cross sections. This paper models the shape of LM-IRSL signals using a recently proposed kinetic model, which describes localized electronic recombination in donor–acceptor pairs of luminescent materials. Within this model, recombination is assumed to take place via the excited state of the donor, and nearest-neighbor recombinations take place within a random distribution of centers. The model has been used previously successfully to describe both thermally and optically stimulated luminescence (TL, OSL). This paper shows that it is possible to obtain approximate solutions for the distribution of donors in the ground state as a function of two variables, time and the distance between donors and acceptors. Approximate expressions are derived for several possible modes of optical and thermal stimulation, namely TL, OSL, linearly modulated OSL (LM-OSL), LM-IRSL and isothermal TL (ITL). Numerical integration of these expressions over the distance variable yields the distribution of remaining donors at any time t during these experimental situations. Examples are given for the derived distributions of donors in each experimental case, and similarities and differences are pointed out. The paper also demonstrates how LM-IRSL signals in feldspars can be analyzed using the model, and what physical information can be extracted from such experimental data. The equations developed in this paper are tested by fitting successfully a series of experimental LM-IRSL data for Na- and K-feldspar samples available in the literature. Finally, it is shown that the equations derived in this paper are a direct generalization of an equation previously derived for the case of ground state tunneling.     

Infrared (IR) stimulated luminescence from modern bricks in retrospective dosimetry applications

It has frequently been observed that certain roof tiles and bricks, especially from relatively modern European buildings, do not contain enough quartz grains in a suitable grain size range to permit dose reconstruction using thermoluminescence (TL) or optically stimulated luminescence (OSL) methods. In this paper the feasibility of using infrared-stimulated luminescence (IRSL) on the feldspar fraction of such bricks and tiles has been investigated. Appropriate preheating treatments were employed in order to select the most stable signals, and procedures were developed to enhance the signal to noise ratio. The possible effect of anomalous fading under application of these procedures was tested. In the dose range above 100 mGy, it has been demonstrated that using IRSL on the feldspar fraction of such material provides a feasible alternative to the use of green-light-stimulated luminescence (GLSL) on the quartz fraction, for the purposes of retrospective dosimetry. Furthermore, since the use of IRSL as described in this paper involves the measurement of polymineral fine grain fractions of bricks, a technique for the calibration of the built-in β source against the γ source in Secondary Standard Dosimetry facilities for routine use of the technique is described.     

Relative response of TL and component-resolved OSL to alpha and beta radiations in annealed sedimentary quartz

Knowledge of the relative luminescence response to alpha and beta radiation is very important in TL and OSL dating. In the present study the relative alpha to beta response is studied in a sedimentary quartz sample, previously fired at 900 °C for 1 h, in the dose region between 1 and 128 Gy, for both thermoluminescence (TL) and linearly modulated optically stimulated luminescence (LM – OSL). The LM – OSL measurements were performed at room temperature and at 125 °C. All OSL signals were deconvolved into their individual components. Comparison of OSL curves after alpha and beta irradiation strongly supports that quartz OSL components follow first order kinetics in both cases. In the case of TL, the relative alpha to beta response is found to be very different for each TL glow-peak, but it does not depend strongly on irradiation dose. In the case of LM – OSL measurements, it is found that the relative behaviour of the alpha to beta response is different for three distinct regions, namely the fast OSL component, the region of medium OSL component originating from the TL glow-peak at 110 °C when stimulation takes place at room temperature and finally the region of slow OSL component. Following stimulation at ambient temperature, the relative alpha to beta response of all components was not observed to depend significantly on dose, with the value of ratio being 0.03 and a tendency to decrease with increasing dose. However, in the case of measurements performed at 125 °C, the relative response of the fast components is much enhanced, and for the remaining components it increases with increasing dose. Special care must be taken to examine the relative alpha to beta response of the fast component at 125 °C which contrasts the relative response of the TL peak at ca. 325 °C. The implications for the dating of annealed quartz are also briefly discussed.     

SrSO4:Eu磷光体的光释光特性

研究了通过掺杂得到的SrSO4:Eu(01mol%)的粉末样品的光释光(OSL)特性.用90Sr的β射线辐照0116—116kGy后，测定了恒定光源激发的光释光发光曲线(CW-OSL)和线性光源激发的光释光发光曲线(LW-OSL)，对发光曲线分析均得到了四种陷阱成分.采用复合作用响应函数得到SrSO4:Eu辐射剂量响应为线性-亚线性.测量了温度对OSL信号的影响，结果表明OSL信号的温度稳定性很好，最灵敏读出温度约为180℃，说明这时OSL信号来自热激发和光激发的共同作用.用60Coγ辐照100Gy后，测量了热释光(TL)三维光谱，确定了发光波长主要位于375nm，可以确定这是来自于Eu2+能级跃迁的发光. 关键词： 光释光 热释光 SrSO4:Eu     

Comparison of ‘blue’ and ‘infrared’ emission bands in thermoluminescence of alkali feldspars

Dating quaternary sediments by thermoluminescence (TL) or optically stimulated luminescence (OSL) calls for a detailed knowledge of the luminescence of feldspars. TL of the various alkali feldspars ((K, Na) Si₃AlO₈) display many common features, and some of these cause great difficulties for dating. After long storage following ionizing irradiation, the TL of most alkali feldspars is known to fade away by “anomalous fading”, which is incompatible with dating. This effect had been attributed to tunnel recombination. Following irradiation, a very intense tunnelling afterglow is observed at temperatures down to liquid nitrogen, in accordance with the observed rate of fading. This emission has a Gaussian spectrum entirely in the infrared (IR) with a maximum at 1.7 eV. It displays an important thermal quenching from 77 to 300 K. Its intensity is related with the ‘disorder’ of the crystal lattice. At higher temperatures, in TL proper, two emission bands can be separated. One is the well-studied complex visible emission, distributed over the spectral region from UV to orange, but mostly ‘blue’. The other is the ‘infrared’ band already observed at lower temperatures, which is attributed to Fe³⁺ ions. These two bands are clearly separated, with the spectral maxima, respectively, below and above 600 nm. They have also different kinetics, the glow peaks temperatures are different. But these two different bands are also coupled in many ways, they have parallel growth and fading. With ‘disordered’ feldspars, the ‘blue’ emission displays anomalous fading, which is stronger than that of the ‘infrared’. The infrared emission is more stable, which may be interesting for the purpose of dating.     

Effects of thermal treatments on luminescence features of three natural feldspars

The effects of prior infrared stimulation on the TL emission of three feldspar minerals (albite, sanidine and orthoclase) were studied. Different reductions in the TL signal were observed in the three samples: albite (Na-rich feldspar) was only partially affected by stimulation while there was an important decrease of TL signal in sanidine and orthoclase (K-rich and intermediate K–Na feldspars). A similar behaviour was also detected when the samples were illuminated at different temperatures. Moreover, when the IR stimulation was performed at temperatures below 100 °C, there was a charge transfer effect (PTTL) that progressively rose, moving from albite to sanidine to orthoclase. A dose recovery experiment was also performed, varying both preheat and measurement temperature. Our results are a further confirmation of the complexity and variability of the luminescence processes in feldspars. They also indicate that the luminescence characteristics of the albite we dealt with are particularly useful for dosimetric application.     

Spectral information from minerals relevant for luminescence dating

The paper reviews basic spectral features of luminescence from minerals used in dating and allied research. Luminescence production is a result of multiple interactions within the imperfect crystal lattice and spectral information is not limited to the emission of light. Results of spectral investigations of luminescence emission during thermal stimulation (TL) or optical stimulation (OSL) form the main part of the paper. However, information on luminescence excitation and light absorption spectroscopy is also presented and possible links between luminescence production in minerals and particular lattice defects are considered. Quartz and feldspars, the most commonly used minerals, receive special attention, but the review includes other materials such as polymineral fine-grained fractions from sediments, zircon, calcite and other salts (halite, sulfate), meteorites, flint, volcanic materials (obsidian, tephra), ceramics and metallurgical slags. Although a wide range of different luminescence emission wavebands occur, it can be shown that certain emissions dominate in particular materials. Basic dosimetric properties are often known just for single emission wavebands of a particular mineral, and are listed in this case. The paper also aims to provide a starting point and inspiration for the study of other TL and OSL emissions, with particular regard to their potential and suitability for dating and related dosimetry tasks. These investigations, involving palaeodose determination based on an emission waveband with known characteristics, need careful separation of the particular emission peak, which may be influenced by its behaviour during the dating procedure (sample preparation, irradiation, preheat treatments, luminescence measurements, etc.). Spectral information available in this context and some technical remarks on the experimental conditions will be given to pave the way for conventional TL or OSL measurements in luminescence dating and dosimetry using natural or semi-natural materials.     

The Dependence of IRSL Intensity on Radiation Dose for Samples of Chlorides Contained in Feldspars

The intensity of the luminescence generally increases with radiation dose and measurement of these phenomena can be used to characterise the degree of dependence on beta doses. In this study, in order to test whether this is a significant problem on the optically stimulated luminescence (OSL) studies, the radiation dose response of the OSL signal from samples of chlorides contained in feldspars have been investigated by irradiating the samples with beta doses. The infrared-emitting diodes were used with a wavelength of (880±80) nm, and an IRSL (infrared stimulated luminescence) intensity parametres, m, was described and found m = 1±0.03.     

Recuperation of infrared stimulated luminescence of feldspars

After bleaching the optically stimulated luminescence (OSL) signal to a low residual level, the signal has been found to increase during subsequent storage or preheating. This effect is well known in quartz as “recuperation of OSL after bleaching” (Aitken, M.J., Smith, B.W., 1988. Optical dating: recuperation after bleaching. Quat. Sci. Rev. 7. 387–393.). A better understanding of recuperation in feldspars could help the dating specialist, because this process might be different from the recuperation observed in quartz. This paper highlights a few examples of a larger study, which cannot be shown here in complete detail. We carried out a recuperation study of infrared-stimulated luminescence (IRSL) of different feldspars from a mineral collection, mainly alkali feldspars and one albite. The samples were irradiated with doses of 200, 1000 and 2500 Gy in a ⁶⁰Co gamma cell. Subsequently, the samples were stored in the dark at room temperature (3 weeks up to 6 months, depending on the applied dose), so that the very intense irradiation-induced phosphorescence can decrease for many orders of magnitude. The emitted OSL was measured through detection filters also used in dating (Schott UG 11, Hoya U 340 for detection of near UV-emissions and Schott BG 39 for detection in the visible range). Recuperation times up to 100 days were used. The recuperated-OSL emissions were measured either with the optical filters mentioned above or with a modified experimental set-up using a variable interference filter with a continuous detection range from 400 to 700 nm. In some feldspars very intense recuperation signals (up to 100% and more of the initial signal) were observed when optical stimulation was performed with IR and broadband detection using the BG 39 or when detection was carried out in the near ultraviolet region. The IRSL emissions at 410 and 560 nm, measured with the interference filter, showed no recuperation despite a clearly detectable first shine-down.     

Improving the TT-OSL SAR protocol through source trap characterisation

Thermally-transferred optically stimulated luminescence (TT-OSL) extends the age range of OSL dating using quartz. A set of experiments have been undertaken to determine the kinetic parameters of the TT-OSL source traps, and this information has been used to propose an improved TT-OSL single aliquot regenerative (SAR) dose protocol. By combining together OSL and thermoluminescence (TL) measurements on fine-grained quartz, a correspondence between TL peaks and the TT-OSL signal is found. The thermal stability of the main TT-OSL trap was estimated by applying Hoogenstraaten’s method and allowing for thermal quenching; this predicts a lifetime of 4.5 Ma at 10 °C. A set of experiments were undertaken to refine the treatment needed at the end of each SAR cycle to erase the previously acquired TT-OSL signal. An improved TT-OSL SAR protocol using this treatment is proposed, and it is tested on quartz from a young Holocene sample. These tests yielded excellent recycling ratios and excellent dose recovery.     

Comparison of the properties of various optically stimulated luminescence signals from potassium feldspar

Various optically stimulated luminescence signals from K-feldspar have been used to determine the equivalent doses of sediment samples. Understanding the properties of these optical signals is critical to evaluate their applicability and limitations to optical dating. In this paper, some properties of IRSL, post-IR OSL and post-IR IRSL signals (detected in the UV region using U-340 filters) from a museum sample of K-feldspar were investigated by analyzing the relationships between optical and TL signals, and the effect of optical bleaching and heating on optical signals. The trap parameters of the different optical signals were calculated using the pulse annealing method. The results show that this sample exhibits two regenerated TL peaks at ～140 and ～330 °C. Corresponding to the low temperature TL peak, the OSL and post-IR OSL signals appear to be more associated with lower temperature TL than the IRSL signal measured at 50 °C. Corresponding to the high temperature TL peak, the post-IR IRSL signals mainly originate from the more thermally stable traps associated with the high temperature TL, compared with the IRSL and post-IR OSL signals. However, the post-IR IRSL_225 °C signal is shown to be hard to be bleached by blue light and simulated sunlight, compared with the IRSL_50 °C and low temperature post-IR IRSL signals. The implication for optical dating is that the elevated temperature post-IR IRSL signals can be preferentially applied over other signals from K-feldspar, but it is desirable that the effectiveness of the pre-depositional zeroing of these signals is assessed.     

Luminescence sensitivity changes in quartz as a result of annealing

Retrospective dosimetry using optically stimulated luminescence (OSL) on quartz extracted from (for example) bricks needs to account for strong OSL sensitivity changes that are known to occur depending on the previous thermal treatment of the sample. Non-heated quartz exhibits OSL orders of magnitude less per unit radiation than that for heated material. The reason these temperature-induced sensitivity changes occur in quartz is presently not well understood. This phenomenon is also seen in the related area of luminescence dating in which sedimentary quartz and quartz from heated archaeological samples show very different OSL sensitivities. In this paper we report on studies of the effects of high temperature annealing on the OSL and phototransferred TL (PTTL) signals from sedimentary and synthetic quartz. A dramatic enhancement of both OSL and PTTL sensitivity was found especially in the temperature range 500–800°C. Computer simulations of the possible effects are shown to produce data that agree in all essential details with the experimental observations. It is further demonstrated that the enhanced OSL sensitivity as a function of annealing temperature is not a pre-dose effect.