Empirical insights into multi-grain averaging effects from ‘pseudo’ single-grain OSL measurements

In this study we assess the signatures of multi-grain averaging effects for a series of sedimentary samples taken from the archaeological site of Hotel California, Atapuerca, Spain. We focus on the special case of equivalent dose (D_e) measurements made on single-grain discs that contain more than one quartz grain in each of the individual grain-hole positions with the aims of (i) providing insight into the nature and extent of averaging effects in very small multi-grain aliquots of sedimentary quartz, and (ii) assessing the suitability of ‘pseudo’ single-grain D_e measurements for this particular dating application. Pseudo single-grain OSL measurements made on standard discs loaded with 90–100 μm grains (equivalent to ～30 grains per hole) yield significantly different D_e distribution characteristics and finite mixture model (FMM) burial dose estimates compared with single-grain OSL measurements. Grains with aberrant luminescence behaviours, which are routinely rejected during single-grain analysis, exert strong averaging effects on the pseudo single-grain and multi-grain aliquot D_e distributions. Grain-hole averaging effects arising from pseudo single-grain measurements also give rise to ‘phantom’ dose components and are apt to provide bias assessments of quartz signal characteristics and grain type classifications. Though this is a site-specific study, it serves as a cautionary note for interpretations of other pseudo single-grain OSL and D_e datasets – particularly those obtained from measurements of discs containing several tens of grains per hole and those derived from complex depositional environments. The use of custom single-grain discs drilled with smaller sized grain holes is recommended as a means of limiting grain-hole averaging effects when dealing with very fine (<180 μm) sediments.     

Na-rich feldspar as a luminescence dosimeter in infrared stimulated luminescence (IRSL) dating

One of the challenges in dating rock surfaces is the choice of the luminescence mineral. Although quartz is the preferred dosimeter in sediment dating, it is often not sufficiently sensitive when extracted from solid rocks. The intensity of signals from feldspars tends to be much less dependent on geological origin and erosion history, but the dosimetry of K-rich feldspar grains extracted from rocks is complicated because the internal dose rate is very dependent on the original feldspar grain size. The in situ grain size information is lost during the crushing process used to separate the grains for measurement. This latter problem does not apply to Na-rich feldspar because of the absence of internal radioactivity.The potential application of Na-rich feldspar as a luminescence dosimeter for the IRSL dating of rock surfaces is investigated using a variety of sediment samples from different geological settings for which independent age control is available. The blue and yellow luminescence emissions are measured for IR stimulation at 50 °C (IR₅₀), and post-IR IR stimulation at 290 °C (pIRIR₂₉₀). Thermal stability experiments imply that the corresponding signals in both emissions have comparable thermal stabilities and that all signals have similar recombination kinetics and are thermally stable over geological timescales. The IR₅₀ doses measured using blue and yellow emissions are similar to or lower than quartz doses while pIRIR₂₉₀ blue doses are higher than those from yellow emission and quartz doses. The fading rates measured for the IR₅₀ signals are ∼3%/decade larger than those measured for the pIRIR₂₉₀ signals in both yellow and blue emissions. Furthermore the average fading rates of both yellow signals are ∼3%/decade higher than the corresponding fading rates of the blue signals. However, there is no detectable correlation between fading rates and the measured D_e values. The residual doses measured from the laboratory-bleached samples and a modern analogue suggest that the IR₅₀ signals in both blue and yellow emissions bleach to the same degree, as do the corresponding pIRIR₂₉₀ signals, and that there is no significant naturally-unbleachable residual dose observed using these signals. Neither anomalous fading nor incomplete bleaching explains the observed dose discrepancy between the two emissions. Eight uncorrected and fading-corrected ages are calculated for each sample based on all four signals, using the dose rate relevant to Na-rich feldspar extracts (i.e. ∼3% K). The IR₅₀ and pIRIR₂₉₀ blue ages were also calculated assuming a dose rate based on 12.5% internal K (i.e. assuming that the blue signals were mainly derived from contamination by K-rich feldspar). The latter pIRIR₂₉₀ blue ages are in agreement with the expected age control, raising the possibility that this signal originates mainly from K-rich feldspar contamination in our Na-rich fractions, and thus is not so useful in the luminescence dating of rock surfaces. On the other hand, the pIRIR₂₉₀ fading-corrected ages based on the yellow emission are consistent with the independent age controls; higher preheat and stimulation temperatures may result in more stable yellow signals from Na-rich feldspar extracts from rocks, and so reduce the size of the fading correction. We conclude that, because this signal avoids the dosimetry difficulties of K-rich feldspar extracts, it has considerable potential in the IRSL dating of rock surfaces.     

The estimation of basic experimental parameters in the fine-grained quartz multiple-aliquot regenerative-dose OSL dating of Chinese loess

The sensitivity-corrected multiple-aliquot regenerative-dose (MAR) protocol provides a reliable approach for fine-grained quartz optically stimulated luminescence (OSL) dating. For reliable estimation of the equivalent dose (D_e), we investigated certain basic experimental parameters in the fine-grained quartz MAR OSL dating of Chinese loess. (1) For suitable bleaching of the natural OSL signal of the regenerative-dose aliquots, the effect of bleaching duration using sunlight, SOL2 and blue LEDs on D_e was studied, and it is found that the appropriate method is a short-duration SOL2 (e.g. 5 min) or blue LEDs (e.g. 60 s) bleaching. (2) To select the appropriate test dose, the relationship between the test dose and D_e was investigated based on three samples having D_e values of approximately 11, 31 and 137 Gy respectively. It is suggested that the test dose for sensitivity correction may be limited to less than approximately 10–20 Gy. (3) Three commonly used fitting modes for quartz OSL growth curve were compared at three regenerative-dose scales. The results indicate that the mode of two saturating exponential functions plus a constant is appropriate and universal. (4) The comparison of D_e values derived using OSL approach with those obtained using the recuperated OSL (ReOSL) protocol shows that the reliable D_e estimation in the fine-grained quartz MAR OSL dating of Chinese loess may be limited to less than approximately 300 Gy. (5) The comparison of growth curves for 18 samples from the Weinan, Xifeng and Jingyuan sites shows that it is feasible to construct a standardized growth curve (SGC) for fine-grained quartz OSL signal in the Chinese Loess Plateau (CLP).     

Bleaching of the post-IR IRSL signal from individual grains of K-feldspar: Implications for single-grain dating

Post-IR IRSL (pIRIR) signals from K-feldspar grains measured at elevated temperatures are increasingly being used for dating sediments. Unfortunately the pIRIR signal from K-feldspars bleaches more slowly than other signals (e.g. OSL from quartz) upon exposure to daylight, leading to concerns about residual signals remaining at deposition. However, earlier studies have not assessed whether the pIRIR signal bleaches at the same rate in all feldspar grains. In this study laboratory bleaching experiments have been conducted and for the first time the results show that the rate at which the pIRIR signal from individual K-feldspar grains bleach varies. To determine whether grain-to-grain variability in bleaching rate has a dominant control on equivalent dose (D_e) distributions determined using single grains, analysis was undertaken on three samples with independent age control from different depositional environments (two aeolian and one glaciofluvial). The D_e value determined from each grain was compared with the rate at which the pIRIR₂₂₅ signal from the grain bleaches. The bleaching rate of each grain was assessed by giving a 52 Gy dose and measuring the residual D_e after bleaching for an hour in a solar simulator. There is no clear relationship between the rate at which the pIRIR₂₂₅ signal of an individual grain bleaches and the magnitude of its D_e. It is concluded that variability in the bleaching rate of the pIRIR₂₂₅ signal from one grain to another does not appear to be a dominant control on single grain D_e distributions.     

Identifying well-bleached quartz using the different bleaching rates of quartz and feldspar luminescence signals

When dating older sedimentary deposits using quartz, there are no unambiguous methods for identifying the presence of incomplete bleaching. Current statistical analysis of dose distributions depends entirely on the assumption that incomplete bleaching and mixing are the main causes of any excess dispersion in the distribution; the only existing way to test this assumption is using independent age control. Here we suggest a new approach to this question, based on the differential bleaching rates of quartz and feldspar luminescence signals. We first present data that confirm the differences in relative bleaching rates of quartz optically stimulated luminescence (OSL) and feldspar luminescence stimulated at 50 °C by infrared light (IR₅₀) and feldspar luminescence stimulated at 290 °C by infrared light after a stimulation at 50 °C (pIRIR₂₉₀), and use recently deposited samples to determine the likely significance of the difficult-to-bleach residual feldspar signals in non-aeolian samples. For a set of mainly Late Pleistocene non-aeolian sediments, large aliquot quartz doses are then used to predict feldspar doses (based on a knowledge of the sample dose rates). The differences between observed and predicted feldspar doses as a function of the quartz dose, combined with a conservative assumption concerning the relative feldspar and quartz residual signals after natural bleaching prior to deposition, are used to identify those samples for which the quartz is very likely to be well bleached (20 out of 24). Two of these apparently well-bleached samples are then examined using single-grain quartz dose distributions; one of these is consistent with the well-bleached hypothesis, and one indicates poor bleaching or a multi-component mixture. However, independent age control makes it clear that the large aliquot data are more likely to be correct. We conclude that a comparison of quartz and feldspar doses provides a useful independent method for identifying well-bleached quartz samples, and that it is unwise to apply statistical models to dose distributions without clear evidence for the physical origins of the distributions.     

The interpretation of quartz optically stimulated luminescence equivalent dose versus time plots

Numerical modelling has shown that the form of the quartz OSL shine plateau (hereafter ‘D_e(t)-plot’) is influenced by the effects of phototransferred TL in the ∼110°C region. It is suggested also that the presence of multiple OSL components (as described by Bailey, Smith and Rhodes, 1997. Partial bleaching and the decay form characteristics of quartz OSL. Radiat. Meas., 27, 123–136; Bailey, 1998. The form of the optically stimulated luminescence signal of quartz: implications of dating. Unpublished PhD thesis, University of London) affects the form of the D_e(t)-plot. Laboratory measurements of a fully reset and artificially dosed sample yielded non-flat D_e(t)-plots, the deviation being greater for the larger of the two simulated palaeodoses, in accordance with theoretical predictions. It is suggested that the so-called ‘shine plateau’ test is of limited use in assessing the bleaching history of quartz sediments.     

Spatially-resolved thermoluminescence from snail opercula using an EMCCD

In recent years opercula of the snail species Bithynia tentaculata have been shown to emit thermoluminescence (TL) signals that can be used to determine equivalent dose, and may be capable of dating events throughout the entire Quaternary period. Concentric growth lines are a notable feature of almost all B. tentaculata opercula, but it is not known whether the luminescence emitted by the opercula is influenced by these structures. This study uses a newly developed EMCCD imaging system to measure the TL signals from opercula. A combination of microscopic analysis of the opercula using visible imagery, and measurement of the TL using the EMCCD system has been undertaken. Variations in TL intensity and equivalent dose (D_e) are seen, but the two are not correlated. Changes in TL intensity broadly mimic the concentric growth structures, but the largest variations in intensity are between different margins of the opercula, not individual growth bands. The EMCCD system makes it possible to produce a two dimensional map of the D_e measured from an operculum. Dose recovery experiments give D_e values that are consistent with each other across the whole opercula. Measurement of the D_e arising from irradiation in nature shows significant variability across a single operculum, but at present the reason for this variability is unknown.     

Luminescence sensitivity changes of quartz by bleaching,annealing and UV exposure

The sensitivities of quartz luminescence signals to dose were studied after ionizing irradiation, ultraviolet (UV) exposure and different annealing conditions. The relationship between the 110 v °C thermoluminescence (TL) and optically stimulated luminescence (OSL) were studied on the same aliquot by looking at the ratio of both signals created by a test dose. It is suggested that the sensitivity changes of both signals are closely related, but not identical. Significant differences are observed when annealing to temperatures higher than 500 v °C. A modified model was proposed to interpret the observations. The similarity is interpreted as the same R hole centers are shared by both signals, whereas 110 v °C TL only uses additional R hole centers. Dramatic changes in luminescence sensitivity for quartz relate to the phase changes.     

Tailoring red-green-blue emission from Er3+, Eu3+ and Tb3+ doped Y2O3 nanocrystals produced via PVA-assisted sol-gel route

Y₂O₃ luminescent nanoparticles were synthesized via PVA-assisted sol-gel method and their structural and optical properties were investigated. Effects of rare earth (Er³⁺, Eu³⁺ and Tb³⁺) doping on luminescence properties of the produced nanophosphors have been investigated under NIR (800 nm) and UV (240–300 nm) excitation. Intense infrared to red and green emissions were observed and a weak blue upconverted luminescence was also detected. Moreover, it was observed that changing the doping ions, the color emitted by the samples could be modified and different combinations of UV excitation and doping produced effective white light emissions. The obtained results demonstrate that PVA-assisted sol-gel is an effective methodology for the synthesis of rare-earth doped Y₂O₃ nanophosphors.     

Reply to the paper “comments on the theory of phase-conjugated waves”, by E. Wolf and W.H. Carter

The NH₄Br crystal is irradiated simultaneously with a modulated red light and a steady UV light in the region of the fundamental absorption band. The resulting recombination luminescence of electrons with V_K centers is phase-sensitively detected, and compared with the emission which is directly excited by UV light. From measurements of the excitation spectra for recombination luminescence, it is pointed out that the dissociation of free excitons occurs efficiently in NH₄Br.     

Improving the accuracy and precision of equivalent doses determined using the optically stimulated luminescence signal from single grains of quartz

Optically stimulated luminescence (OSL) measurements of quartz are widely used to measure equivalent dose (D_e). At radiation doses above ～100 Gy, saturation of traps results in a decrease in the rate of growth of the OSL signal, and this makes calculation of D_e increasingly difficult. A series of dose recovery experiments was undertaken using single grains of quartz from Kalambo Falls, Zambia to explore saturation of single grains. When the OSL signal from many grains is averaged, the characteristic dose (D₀) is 47 Gy, typical of published values for quartz. However, D₀ for individual grains varies from ～10 to 100 Gy. Doses up to two times the average D₀ could be accurately recovered, but above this dose the D_e became increasingly underestimated. Overdispersion for this type of experiment should be zero, but was observed in all data sets; furthermore the value of overdispersion increased with D_e. An additional acceptance criterion, the Fast Ratio, is suggested for single grain OSL analysis. This criterion assesses the relative contribution of the fast component of the OSL signal. Including this as an additional acceptance criterion leads to an improved precision, with overdispersion reduced to zero, and improved accuracy in dose recovery at high doses.     

The problem of dating quartz 2: Synchrotron generated X-ray excited optical luminescence (XEOL) from quartz

The luminescence emission of quartz is used in optically stimulated luminescence dating (OSL), however the precise origins of the emission are unclear. A suite of quartz samples were analysed using X-ray excited optical luminescence (XEOL). Radiation dose effects were observed whereby the UV emissions (3.8 and 3.4 eV) were depleted to the benefit of the red emission (1.9–2.0 eV). Samples were excited at ∼7 keV. Understanding why some quartz emit light more brightly than others will increase the efficiency and precision of OSL analyses.     

Spectral characteristics of intense red luminescence in Pr:Y2O3 nanophosphor on UV excitation

Detailed structural and spectroscopic characterizations of Pr:Y₂O₃ nanophosphor have been carried out. On ultraviolet light (at 266?nm) excitation, intense red emission along with weak emissions in blue, green and infrared regions have been observed. The phenomena for the observed emission have been thoroughly explained in the present work and it was finally concluded that the?direct excitation through low-lying 4f¹5d band of Pr³⁺ ions and through the conduction band of Y₂O₃ nanophosphor are the main channels for the observed emissions. The calculated quantum efficiency (QE) for the red emission is found to be ~80?% while the CIE coordinates are (0.65, 0.34) quite close to the standard values. These studies clearly indicate that Pr:Y₂O₃ nanophosphors are promising and futuristic red luminescent material for the development of various display devices and UV detectors. Time resolved spectroscopy has been further used to investigate luminescence dynamics.     

Effects of substrate on surface morphology, crystallinity, and photoluminescence properties of sputtered ZnO nano films

Effects of substrate on crystallinity, surface morphology, and luminescence properties of radio frequency sputtered zinc oxide (ZnO) thin films were investigated. A variety of materials such as Si (100), Si (111), Al₂O₃, quartz, and silicon carbide (SiC) wafers were examined as substrates for deposition of ZnO thin films. The results showed smooth and uniform growth of c-axis orientation films. The thickness of the layers was about 50 nm. The average grain sizes of films were about 10, 13, and 12 nm for Si (111), quartz, and SiC samples, respectively. The deposited film on Al₂O₃ showed the largest grain size, about 500 nm. Grazing incidence x-ray diffraction patterns of the samples revealed that sputtered layers on Al₂O₃ and quartz had better crystallinity with higher peak at (002) orientation compared to Si and SiC substrates. Moreover, the Al₂O₃ sample exhibited a weak peak at position of (100) planes of ZnO too. The photoluminescence spectra of the samples showed a typical luminescence behavior with a broad UV band, including a main peak at around 388 nm and a weak shoulder peak at around 381 nm, corresponding with bound excitonic recombination and free excitonic recombination, respectively. The luminescence peak revealed that the intensity of UV emission is not necessarily dependent on the grain sizes and the micro-structural quality of ZnO films.     

Probing luminescence centers in Na rich feldspar

In contrast to the detailed investigations on the dosimetric electron trap in feldspar only little has been done to understand the luminescence centers. We use a comparison of multiple spectroscopic techniques, site selective photoluminescence spectroscopy and time resolved measurements to further our understanding of the luminescence mechanisms and recombination sites, in a sample of Na rich plagioclase feldspar (oligoclase). Both the UV and violet–blue emissions show resonant excitations arising from a distribution of energy levels. We propose, contrary to the general understanding, that the green emission may not arise from Mn²⁺ in our sample and that photoionisation of this centre may be possible by excitation to the band tail states. The deep red emission is tied to the Fe³⁺, and the exponential rise in the UV excitation efficiency of this centre is discussed in the context of the band-tail model.     

Red luminescence of ZnS: Fe crystals

In order to elucidate the nature of the red emission band at 660 nm in ZnS: Fe crystals, the equilibrium luminescence, the thermoluminescence and the photoinduced EPR signals were measured, using UV, or the simultaneous UV + IR excitations. In addition, the polarization properties and the light-pressure shift of the red luminescence were studied. On the basis of the obtained results and of the data reported in the literature and concerning the red and IR emissions in ZnS: Fe a donor-acceptor model is proposed, in which the transition Cl^2?→Fe³⁺ would give rise to the 660 nm band.     

Investigations of the post-IR IRSL protocol applied to single K-feldspar grains from fluvial sediment samples

The post-IR IRSL protocol with single K-feldspar grains was applied to three samples taken from a fluvial sedimentary sequence at the archaeological site of the Dali Man, Shaanxi Province, China. K-feldspar coarse grains were extracted for measurement. Approximately 30–40% of the grains were sufficiently bright to measure, and after application of rejection criteria based on signal strength, recuperation, recycling ratio and saturation dose, ～10–15% of the grains were used for D_e calculation. The relationship of signal decay rate and form of D_e(t) with the recovery dose were investigated. The dose recovery ratios of the samples after initial bleaching with the four different light sources were within uncertainties of unity. No anomalous fading was observed. The over-dispersion of the recovered dose and D_e values were similar, suggesting neither incomplete resetting of the post-IR IRSL signals nor spatially heterogeneous dose rates significantly affected the natural dose estimates. The values of D_e obtained with the single K-feldspar grain post-IR IRSL protocol were in the range ～400–490 Gy. Combining all of the measured single-grain signals for each of the individual samples (into a ‘synthetic single aliquot’) increased the D_e estimates to the range ～700–900 Gy, suggesting that the grains screened-out by the rejection criteria may have the potential to cause palaeodose over-estimation, although this finding requires a more extensive investigation. Thermally transferred signals were found in the single K-feldspar grains post-IR IRSL protocol, and the proportion of thermally transferred signal to test-dose OSL signal (stimulation at 290 °C) from the natural dose was higher than from regenerative doses, and the proportion was grain- and dose-dependent. As such, TT-post-IR IRSL signals at 290 °C have the potential to cause dose underestimation, although this may be reduced by using larger test-dose irradiations. Our study demonstrates considerable potential in the post-IR IRSL method in providing chronological control in studies relevant to human evolution in the later-Pleistocene.     

Retrospective dosimetry using Japanese brick quartz: A way forward despite an unstable fast decaying OSL signal

Quartz extracted from heated bricks has been previously suggested for use in dose estimation in accident dosimetry, but this technique has never been applied before to Japanese quartz which often has unusual OSL characteristics. In this study the optically stimulated luminescence (OSL) characteristics of quartz extracted from a Japanese commercial red brick produced by Mishima – Renga – Seizoujyo Co. are studied. These companies are based in the Aichi Prefecture (capital Nagoya), which accounts for about half of the red brick production in Japan. A comparison of TL (thermoluminescence) and OSL signals has been carried out towards identification of common source traps. It is observed that OSL from Japanese brick quartz shows unusual luminescence characteristics; in particular, the initial fast decaying OSL signal contains a dominant (>90%) thermally unstable component related to the 85 °C TL peak, which necessitates a prior heat treatment. A single-aliquot regenerative-dose (SAR) protocol is developed and tested using thermal treatments intended to isolate a stable dosimetric signal. A minimum detection limit of ～65 mGy is then estimated using this protocol. Following irradiation using ⁶⁰Co and ¹³⁷Cs, dose–depth profiles were measured on two different commercial brick types (Mishima – Renga – Seizoujyo Co. and Hase – Renga Co.) with 5 Gy and 10 Gy surface doses. The profiles derived from the two sources were readily distinguishable. It is concluded that the OSL signals from the two types of Japanese brick quartz examined here can be used to derive precise estimates of accident dose, and, possibly to distinguish between sources of gamma radiation in a nuclear accident.To our knowledge, this is the first report on the existence of an unstable fast decaying OSL signal in quartz derived from bricks, and demonstrates a way forward with such samples in retrospective dosimetry.     

On the intrinsic accuracy and precision of the standardised growth curve (SGC) and global-SGC (gSGC) methods for equivalent dose determination: A simulation study

In optically stimulated luminescence (OSL) dating, the single aliquot regenerative-dose (SAR) method has been used extensively for determining equivalent doses (D_e) in quartz. A variation of the SAR method is the “standardised growth curve” (SGC) method, which has been used as an efficient procedure to save measurement time during dating studies. During the application of the SGC method one establishes the SGC and calculation of the D_e of an aliquot requires only measurement of the standardised natural dose signal. Recently, a “global standardised growth curve” (gSGC) method was developed as an improved version of the SGC procedure. During the application of the gSGC method, the growth curves are re-normalised using sensitivity-corrected signal corresponding to one of the regenerative doses. Subsequently the D_e of an aliquot is estimated using the sensitivity-corrected natural dose signal and an additional sensitivity-corrected regenerative dose signal as well as the established gSGC. In the present study, simulations are performed to assess the intrinsic accuracy and precision of the SGC and gSGC D_e estimates. The results of our simulations validate that the gSGC method is intrinsically more precise than the SGC method and is also more accurate for doses greater than 210 Gy. Several factors which affect the reliability of the two methods are investigated.     

Lyoluminescence mechanism of additively and gamma coloured alkali halides in fluorescent and chemiluminescent solutions

Lyoluminescence of gamma irradiated and additively coloured NaCl, NaBr, KCl and KBr crystals when dissolved in fluorescent and chemiluminescent aqueous solutions is investigated. Spectral analysis of the emitted light has shown that lyoluminescence spectra are similar to the fluorescence spectra of these solutions. Luminescence takes place when a fluorescent acceptor is directly excited by a liberated F-centre (hydrated electron e^-_aq) or indirectly by an energy transfer from a released excited halide ion ∥X^-∥¹ (solvated hole after recombination with hydrated electron). Oxygen, in general, has a marked quenching effect on luminescence. In chemiluminescent systems, its presence is essential to provoke luminescence in a sequence of events leading to a fluorescent end product.