Progress and pitfalls of the SAR protocol for the quartz violet stimulated luminescence (VSL) signal: A case study from Sardinia

In the quest for extending the upper age limit of optically stimulated luminescence (OSL) dating of quartz, it was shown that violet stimulated luminescence (VSL) may be a promising candidate. However, difficulties in the application of the single aliquot regenerative dose (SAR) protocol for VSL has been reported in previous studies. In this study, a set of experiments was carried out to investigate the behaviour of the VSL signal under different measurement conditions with the aim to improve the SAR VSL protocol in terms of passing the procedural tests of the SAR protocol, i.e., recycling ratio, recuperation and dose recovery. The validity of an optimised SAR protocol was then evaluated on four coarse-grained quartz samples from Sardinia, for which previously reported OSL and post-IR IRSL ages are available. Our result showed that all measured aliquots meet the recuperation, recycling ratio and dose recovery criteria, indicating that the proposed protocol is suitable for the studied samples. The obtained VSL and reference ages agree within uncertainty (2σ) for most of the samples except one sample with a largest expected equivalent dose of ∼320 Gy, for which the VSL significantly (∼50%) underestimates despite satisfactory dose recovery result. This underestimation is most likely due to trapping sensitivity change between the natural and all subsequent regenerated VSL signals induced by the first preheating in the SAR procedure, which is likely dose dependent. To minimise sensitivity change, the sensitivity-corrected multiple aliquot regenerative dose (SC-MAR) protocol was applied. The SC-MAR protocol yields VSL ages in agreement with reference ages for two samples (1σ); the other two samples show overestimation. We show that the observed age overestimation can be explained by incomplete resetting of the natural signal after 7 days SOL2 exposure used for the SC-MAR procedure. Bleaching experiments confirm variable bleaching behaviour among different samples. However, it is unclear whether this different bleaching behaviour arises from measuring samples with different bleaching histories, mineralogical compositions, or VSL source trap properties.     

Violet stimulated luminescence as an alternative for dating complex colluvial sediments in the Atacama Desert

Luminescence dating has become a key tool in studies of the Quaternary. The typically stable luminescence response of quartz grains and the absence of a significant internal dose, make quartz minerals the preferred dosimeter for monitoring the burial dose in sediments. Unfortunately, the reliability of conventional OSL (optically stimulated luminescence) dating, based on blue stimulation, can be compromised when the luminescence decay is not dominated by a rapidly decaying and stable part of the luminescence signal (i.e. the fast component). On the other hand, standard methods in luminescence dating are limited to ages of a few hundred kiloyears. In this study, violet stimulated luminescence (VSL) has been used as a means to overcome both problems, applied to a series of colluvial deposits in the Atacama Desert, Chile. Quartz from this region, characterized by poor blue-OSL response, showed a reproducible and stable VSL signal capable of recovering given doses up to ∼500 Gy and a saturation dose twice as high as conventional OSL. The VSL response from these samples has been studied in detail and the estimated ages have been compared with an already established chronology for the same site, based on IRSL of potassium feldspar single grains. Results agree for the dose range of the profile studied, ∼100–250 Gy, equivalent to ages of 29–79 ka confirming the suitability of VSL for dating sedimentary quartz with unreliable blue-OSL response and to extend the age range of conventional OSL dating.     

Luminescence dating of the late Quaternary sediments in Hangzhou Bay,China

Coastal plain of Hangzhou Bay, to the south of the present Yangtze Estuary, is closely linked to the evolution of the Yangtze River delta. However, absolute age of Pre-Holocene sediments is limited, which hinders the understanding of this area's environmental evolution. In this study, using optically stimulated luminescence (OSL), single aliquots and single grains of quartz and K-feldspar were used to date the late Quaternary sediments in coastal plain on the southern Hangzhou Bay. The vertical difference in particle size composition render either silt- or sand-sized quartz for dating. Cross-checking of multiple OSL dating methods indicated that the upper ∼65 m recorded the Holocene part of the succession; sediment from a depth of 136.6 m was dated to ∼180 ka. It was found that the single-grain method was more reliable in comparison to single-aliquot age, the former minimized the effect of signal components. Single-grain quartz and K-feldspar luminescence yielded consistent ages at sample depth of 136.6 m (∼160–180 ka), while the latter gave robust age at depth of 115.5 m (∼150 ka). This chronology is in general in accordance with neighbouring cores and can constrain paleomagnetic dating results in those cores. Taking together, the study site has thickest Holocene deposits in comparison to the highland centered around Taihu Lake on the southern Yangtze delta. Moreover, the luminescence characteristics of quartz from different sample depths, behaved differently with respect to luminescence sensitivity, signal components and saturation level, perhaps reflecting varied provenance and weathering characteristics caused by climate change.     

Luminescence dating of marine sediments from the Sea of Japan using quartz OSL and polymineral pIRIR signals of fine grains

Luminescence dating has long been used for chronological constraints on marine sediments due to the ubiquitous dating materials (quartz and feldspar grains) and its applicability over a relatively long time range. However, one of the main difficulties in luminescence dating on marine sediments is partial bleaching, which causes age overestimations. Especially, partial bleaching is typically difficult to be detected in the fine grain fraction (FG) of marine sediments. The recently developed feldspar post-IR IRSL (pIRIR) protocol can detect non-fading signals and thus avoid feldspar signal instability. In the current study, fine grains were extracted from a gravity core in the northern Sea of Japan, and the aim is to test the feasibility of using different luminescence signals with various bleaching rates to explore the bleaching conditions of fine grain fraction in marine sediments. The results suggest that the quartz OSL signal and polymineral pIRIR signals at stimulation temperatures of 150 °C and 225 °C (pIRIR₁₅₀ and pIRIR₂₂₅) of FG were well bleached prior to deposition. The OSL ages were used to establish a chronology for this sedimentary core and the resulting age-depth relationship is self-consistent and comparable with radiocarbon dates. We conclude that different luminescence signals with various bleaching rates can be used to test the bleaching conditions of fine grain fraction in marine sediments; and the luminescence dating can be applied to marine sediments with great potential.     

Testing single-grain quartz OSL methods using sediment samples with independent age control from the Bordes-Fitte rockshelter (Roches d'Abilly site,Central France)

We present quartz single-grain dose distributions for four well-bleached and unmixed sediment samples with independent age control (22–48 ka), from the archaeologically important Bordes-Fitte rockshelter at Roches d'Abilly, France. This site has previously been dated using ¹⁴C AMS dating and standard multi-grain OSL dating using both quartz and feldspar. The effect of rejection criteria usually employed in single-grain dating on dose and over-dispersion is tested using both laboratory irradiated samples and natural samples. It is shown that had these samples been analysed in the absence of other age control, standard modelling decisions based on the shape of single-grain dose distributions would have led to significant misinterpretation of results and a corresponding >40% underestimation in age. If we instead ignore this standard decision process and apply weighted average and mixing models then the most likely results deviate from the expected ages by >10%. Finally, we show that by careful consideration of the luminescence characteristics of individual grains, we are able to obtain good agreement with the independent age control by applying alternative rejection criteria but this is at the cost of reducing the accepted grain population by more than an order of magnitude, with the corresponding inevitable decrease in precision.     

Luminescence and ESR dating of the sedimentary infill from the multi-level cave system of Alkerdi-Zelaieta (Navarre,N Spain)

The finding of Upper Paleolithic engravings in 2016 triggered a multidisciplinary investigation of the Alkerdi cave system (Urdazubi, N Spain). The study of the speleogenetic processes led to the identification of at least 6 paragenetic cave levels with associated sedimentary infill. In order to unravel the timing of changes in the karst dynamics and to get some insights about sediment origin, two sediment samples were collected from cave levels 4 and 1 for numerical dating purpose, using both Optically Stimulated Luminescence (OSL) and Electron Spin Resonance (ESR) methods. One additional modern-age sample was also taken from the entrance of the karst to evaluate the magnitude of the optical bleaching achieved by the quartz grains before entering the cave system. Last, one sample was collected from a flowstone for U-series dating, providing independent age control.OSL measurements were carried out using small quartz multi-grain (MG) and single-grain (SG) Single Aliquot Regenerative-dose (SAR) protocol. Initial Equivalent Dose (D_e) results show evidence of saturated OSL signal for the sample of the higher level (with ∼60% of saturated aliquots). Unlike SA data, SG analyses do not meet the usual quality criteria (e.g., relatively high recuperation ratios, only a few grains with useable signal), suggesting that corresponding dating results should be treated with caution.Hence, both MG and SG TT-OSL and MG ESR methods were subsequently employed, as the corresponding signals are known to have higher saturation levels than OSL ones. ESR analyses were based on the Multiple Centre (MC) approach using the standard multi-grain multi-aliquot additive (MAA) dose method, while TT-OSL measurements were performed following Demuro et al. (2020). The latter, however, did not return any useful results for both samples. MC ESR data show the usual D_e pattern (D_e(Al)>D_e(Ti op. D)>D_e(Ti–H)) indicating that among the three ESR signals analyzed, the Ti–H most likely provides the closest estimate to the true burial age. However, low measurement repeatability and goodness-of-of fit indicate that the reliability of the ESR results may be reasonably questioned.Results derived from this multi-technique dating approach provide the first chronological constraints for the sedimentary infill of the Alkerdi cave system. In particular, they suggest that sediment deposition in Cave Level 4 (ALK-OSL01) occurred around 130 ka, which is in good agreement with the minimum age constraint given by the speleothem (80.5 ± 9.0 ka). In comparison, the young age obtained for sample ALK-OSL02 (5.0 ± 0.9 ka) suggests recent Holocene formation of the lowest cave level 1.Finally, the MG De value obtained for the modern sample is close to zero (<1 Gy), indicating that the OSL signal is almost fully reset at a multi-grain level before entering the cave. Additionally, despite the large De overdispersion measured in this modern sample, the De values are one to two order of magnitude lower than those obtained with the same model in the other two samples. Therefore, the large OSL D_e overdispersion (OD) values of up to 64% obtained for the two samples from Cave Level 4 and 1 are most likely related to re-sedimentation processes inside the cave system.     

ESR dating of optically bleached quartz grains from Plio-Pleistocene to Holocene coastal dune deposits (Wilderness-Knysna area,South Africa): a comparison with luminescence

Five Plio-Pleistocene to Holocene aeolian quartz samples from the coastal dune deposits of the Wilderness-Knysna area (South Africa) previously dated by OSL were selected for ESR dating. Samples were processed following the Multiple Centre approach and using the Multiple Aliquot Additive dose method. Aluminium (Al) and Titanium (Ti) signals were systematically measured in all samples.Our study shows that ESR results obtained for Middle Pleistocene to Holocene samples may be strongly impacted by (i) the presence of a significant high frequency noise in the ESR spectra acquired for the Ti signals and (ii) the choice of the fitting function employed. In particular, if not taken into account, very noisy spectra can lead to a significant overestimation of the true ESR intensity measured for the Ti–H signal. These sources of uncertainty are however not sufficient to remove the ESR age overestimations. Consequently, our results indicate that the Al and Ti ESR signals of these quartz samples have not been fully reset during their aeolian transport.While this work contributes to improve our understanding of the ESR method applied to quartz grains, and especially of the potential and limitations of the Ti signals, it also provides additional baseline data to illustrate the existing variability among quartz samples of different origins or sedimentary context. Our results are consistent with previous studies by confirming that the Ti–H signal shows the best potential for the evaluation of low dose values (<100 Gy for these samples), whereas it becomes inappropriate for the higher dose range, and the Ti–Li–H (option D sensu Duval and Guilarte, 2015) should be used instead.Beyond the methodological outcome, this ESR dating study also provides a useful addition to the existing chronology of the aeolian deposits in this region. In particular, new (and possibly) finite numerical age results were obtained for the two oldest samples, constraining the aeolianite landward barrier dune and the coversand formations to the MIS 10-8 and Pliocene, respectively.     

Testing the accuracy of quartz OSL dating using a known-age Eemian site on the river Sula, northern Russia

Quartz optically stimulated luminescence (OSL) forms the basis for the chronology of Weichselian ice advances in Arctic Eurasia developed over the last few years. There is almost no age control on this chronology before 40 ka, except for some marine sediments correlated with marine isotope stage (MIS) 5e on the basis of their palaeofauna. Results from more southern latitudes have shown that dose estimates based on quartz OSL and the single aliquot regenerative (SAR) dose procedure may underestimate the age of MIS 5e deposits. Here we use the same method to date well-described marine sediments, thought to have been deposited during the very beginning of the Eemian interglacial at 130 ka, and exposed in two sections on the river Sula in northern Russia. Various quality-control checks are used to show that the OSL behaviour is satisfactory; the mean of 16 ages is 112±2 ka (σ=9 ka). This represents an underestimate of 14% compared to the expected age, a discrepancy similar to that reported elsewhere. In contrast to SAR, the single aliquot regeneration and added (SARA) dose procedure corrects for any change in sensitivity during the first OSL measurement. The SARA results are shown to be 10% older than those from SAR, confirming the geological age estimate and suggesting that SAR ages may underestimate older ages (larger doses), despite their good performance in the younger age range.     

Late Quaternary evolution of lower reaches of the Volga River (Raygorod section) based on luminescence dating

The normally-closed Caspian Sea is known for large changes in relative sea-level (of ∼170 m) during the late Quaternary. These transgressive/regressive events influenced the topography, sedimentation and ecosystems of a large area, of up to 1 million km². The Volga River has played an important role in the water balance of the Caspian Quaternary basins but our understanding of the temporal evolution is poorly constrained. Recent studies on the evolution of the Lower Volga have focused mainly on the subaerial sequence of loess-palaeosol series corresponding to a long-duration Caspian low stand (the so-called “Atelian regression” from ∼90 to ∼25 ka). In this study we address, for the first time, the temporal evolution of the Volga River during the late Quaternary, as recorded in the many layers of alluvial sands at the Raygorod reference section. This 50 m high outcrop contains a complicated sequence of different types of interlayered alluvium (channel and floodplain facies), a loess-palaeosol sequence with a weakly developed palaeosol, and marine sediments of the Khvalynian transgression (Chocolate Clay facies). The new chronology, based on 35 samples, is derived using optically stimulated luminescence (OSL) analysis of sand-sized quartz, with support from post-infra-red infra-red stimulated luminescence (post-IR IRSL) from K-rich feldspar grains to date the older parts of the section. The new ages identify five stages of the topography development in the northern parts of the Lower Volga: (1) an MIS 5a flood-plain in deltaic/estuary environments (>90 ka) during a high-stand of the Caspian Sea (Hyrcanian transgression); (2) a transition from deltaic/estuary conditions to a river valley with normal alluvial sedimentation and sporadic stabilization reflected in palaeosol development (80–70 ka); (3) a palaeo-Volga channel migration at elevations of 4–8 m msl during 69–62 ka, evidence of a brief increase in Caspian Sea-level and blocking of the Volga flow; (4) a subaerial stage with high-speed accumulation of loess during MIS 4 to MIS 2, containing one weakly developed palaeosol (MIS 3c) and pedocomplex of three combined palaeosols of the beginning of MIS2 (30–24 ka); (5) a rapid Khvalynian transgression, starting at the Raygorod location at ∼18.3 ka, with relatively weak marine erosion of the top 40–60 cm of loess cover, presumably because of the rapid migration of the coastline in the flat Northern Caspian Lowland.     

Constraining the age of Quaternary megafloods in the Altai Mountains (Russia) using luminescence

Some of the largest catastrophic outbursts of periglacial lakes known in the geological history of the Earth have been identified in the Altai Mountains. Traces of these events are recorded in the form of large terraces, predominantly composed of gravel material with numerous horizons of large boulders and blocks. Determining the age of these large-scale events is difficult due to the lack of suitable material (e.g. organics, well-bleached sand) and the specific genesis of these sediments. The results of cosmogenic radionuclide dating suggest a post-LGM age both for the source of the flood water and for different elements of the catafluvial terraces in the Chuya and Katun river valleys. Nevertheless, the age(s) of catastrophic breakthrough remains controversial. On the basis of a few IRSL ages, and geological and other evidence, some view the event as occurring around MIS 5. In this study, we investigate loess-like loams overlying the catafluvial sediments on the surface of the highest level terrace, ∼200 m above present river level. A total of 24 samples for luminescence dating were obtained, for which the OSL, IR₅₀, and pIRIR_50,290 signals were measured to control the degree of signal zeroing and the dating reliability. The age of the loess in all three pits was from 0.5 ka at the top to 23 ka at the base of the loess strata. From a sand layer in the top of the catafluvial deposits, two ages of ∼85–90 ka were obtained from feldspar pIRIR_50,290. These results provide a minimum pre-LGM age for the geomorphological surface of a major catafluvial terrace in the Altai Mountains.     

ESR dating of glacial moraine deposits: Some insights about the resetting of the germanium (Ge) signal measured in quartz

The electron spin resonance (ESR) dating of tills using germanium-doped (Ge) paramagnetic centers in quartz has advantages over other dating techniques, as quartz is common, processing is easy, and the technique has the potential for dating features several hundreds of thousands years old. ESR dating of moraines is based on the supposition that either subglacial comminution or exposure to sunlight resets the signal. However, actual dating suggests that a signal that is initially present cannot be bleached to zero by grinding alone. We found that grinding coarse samples (0.5–1 mm in diameter) to the mean grain size of fine sand (0.125–0.193 mm) reduced the signal intensity to 53–69% of its original value. From the value of the signal difference, one can devise a correction factor for ESR ages of subglacial sediment. Polymineralic grains are commonly present in till. Exposure of them to sunlight for several days can reduce the signal intensity to 7–8% of its original value within 1–2 mm thick of the sediment surface. However, within 5–8 mm of the sediment surface, exposure to sunlight for over one week only reduced the signal intensity to mean plateau values of 42–50% of the initial value. Mixing upper and lower layers of the samples during exposure to sunlight changed the signal intensity. This suggests that the amount of bleaching varies spatially. Sediments initially deposited at the margins of ice caps or ice sheets and subsequently overridden may have been sufficiently exposed to sunlight to allow ESR dating of moraines. The purity of the quartz and the grain size have significant impacts on signal intensity; intensive purification and the use of a uniform fine sand fraction are thus recommended.     

Tephrostratigraphy and paleoenvironmental variation in late Quaternary core sediments of the southwestern Ulleung Basin, East Sea (Sea of Japan)

Abstract   Data on the late Quaternary tephra layers, tephrostratigraphy, geochemistry and environment were determined in two sediment cores from the southwestern part of Ulleung Basin (East Sea/Sea of Japan), representing marine-oxygen isotope stages 1–3. The cores consist mainly of muddy sediments that are partly interbedded with silty sands, lapilli tephra and ash layers. The lapilli tephra layers (Ulleung-Oki tephra, 9.3 ka) originating from Ulleung Island consist mainly of massive-type glass shards, whereas the ash layers (Aira-Tanzawa ash, 22.0–24.7 ka) derived from southern Kyushu Island are mainly composed of typical plane-type and bubble-wall glasses that are higher in SiO₂ and lower in Na₂O + K₂O than the lapilli tephra layers. Except for the tephra layers, fine-grained sediments throughout the core sections are mostly of marine origin based on geochemical data (C/N ratios, hydrogen index, S2 peak) and Tmax. In particular, organic carbon contents increased during Termination I, probably as a result of an influx of the deglacial Tsushima Current through the Korea Strait.     

On the interest of using the multiple center approach in ESR dating of optically bleached quartz grains: Some examples from the Early Pleistocene terraces of the Alcanadre River (Ebro basin,Spain)

The present work reports the first numerical ages obtained for the two highest fluvial terraces (Qt1 and Qt2) of the Alcanadre River system (Northeastern Spain) representing the earliest remnants of Quaternary morphosedimentary fluvial activity in the Ebro basin. ESR dating method was applied to optically bleached quartz grains and both the Al and Ti centers were measured, in accordance with the Multiple Center approach. The results are overall in good agreement with the existing preliminary chronostratigraphic framework and our interpretation indicate that terraces Qt1 and Qt2 have an ESR age of 1276 ± 104 ka and 817 ± 68 ka, respectively. These data provide some chronological insights on the beginning of the fluvial sedimentary processes in a scenario of incision maintained over Quaternary in the Ebro Basin. These are among the first numerical ages obtained for such high terraces in the Iberian Peninsula.Our results demonstrate the interest of using the Multiple Center approach in ESR dating of quartz, since the two centers provide complementary information, i.e. an independent dose control. The overall apparent consistency between the ESR age estimates and the existing preliminary chronostratigraphic framework may be considered as an empirical evidence that the Ti–Li center may actually work for Early Pleistocene deposits, whereas the Ti–H center shows some clear limitations instead. Finally, these results demonstrate the interest of using ESR method to date Early Pleistocene fluvial terraces that are usually beyond the time range covered by the OSL dating method.     

Test of high sampling density OSL dating of aeolian samples from the south margin of the Tengger Desert using the global standardised growth curve (gSGC) method

Chronostratigraphic records in the drylands of north China provide basic archives to reveal the dynamic connections between climate changes and the behaviour of aeolian systems. However, the interpretation of aeolian chronostratigraphy is not straightforward and may be associated with significant uncertainty due to a number of external and localised forces. Taking into account this complexity of aeolian systems, excluding preservation and sampling bias from palaeoclimatic signals requires that the interpretation of chronostratigraphic records be based on as many dates from as many sites as possible. Optically stimulated luminescence (OSL) dating provides a direct way to date aeolian sediments. However, the determination of equivalent dose (D_e) using the commonly applied single-aliquot regenerative dose (SAR) protocol is relatively time-consuming for samples with burial doses exceeding 50 or 100 Gy.In this study, the global standardised growth curve (gSGC) method is applied to multi-grain aliquots of coarse quartz from various sites covering a wide region of the south margin of the Tengger Desert in north China to rapidly determine D_e for a large number of aliquots and samples. The large between-aliquot variability in the shape of the dose response curve (DRC) is significantly reduced using a least-squares normalisation procedure. The results of a leave-one-out cross-validation (LOOCV) protocol demonstrates that D_e values determined using the gSGC and SAR methods are very consistent with each other up to at least 200 Gy and 400 Gy, for the 90–150 μm and 63–90 μm fractions, respectively. It suggests that the gSGC protocol can be used as an efficient procedure for D_e determination of a large number of aeolian samples from multiple sites. This in turn provides a better constraint for the interpretation of Late Quaternary aeolian chronostratigraphic records in drylands of north China.