Radioluminescence dating of sediments: methodological aspects

Radioluminescence (RL) at 865 nm (1.42 eV) — a characteristic of potassium feldspar — has been applied successfully in the dating of Quaternary sediments. The signal can be interpreted as the infrared (IR)-emitting electron transition into a light sensitive trap. Direct measurement of the electron density is thus possible, and this is the basic advantage of this new method. Further investigations have been carried out to develop a precise and reliable IR-RL dating procedure. Besides the already applied additive dose total bleach technique, that of total bleach regeneration and a combination of both (slide technique) were tested in the dating of different aeolian and waterlaid sediments. New bleaching experiments show that about 10 min of light exposure (about 300–700 nm) is sufficient to reach the saturation level of the IR-RL signal. Palaeodose determinations of recently deposited sediments result, in most cases, in an age equivalent to <6 ka. The results of spectral RL measurements suggest that use of non-spectral-resolving detection systems would require an interference filter to reject the unwanted influence of a red RL emission wave-band.     

Observations of thermal transfer OSL signals in glacigenic quartz

The conclusions of Rhodes and Pownall (Rhodes, E.J., Pownall, L., 1994. Zeroing of the OSL signal in quartz from young glaciofluvial sediments. Radiation Measurements 23, 329–333) were somewhat discouraging for the prospects of using quartz OSL for dating glacigenic sediments, while the more detailed study of Rhodes and Bailey (Rhodes, E.J., Bailey, R.M., 1997. The effect of thermal transfer on the zeroing of the luminescence of quartz from recent glaciofluvial sediments. Quaternary Science Reviews (Quaternary Geochronology) 16, 291–298) provided more encouragement. Specifically, the latter authors were able to account for the relatively high D_e values observed for recent glacigenic (dominantly glaciofluvial) sediments in terms of an anomalously high thermal transfer effect, rather than simply insufficient bleaching prior to deposition. In other locations, the OSL of quartz from glacigenic material appears to provide reliable age estimates, and does not suffer from these effects (Owen, L.A., Richards, B., Rhodes, E.J., Cunningham, W.D., Windley, B.F., Badamgarav, J., Dorjnamjaa, D., 1998. Relic permofrost structures in the Gobi of Mongolia: age and significance. Journal of Quaternary Science 13 (16), 539–548; Richards, B.W., Owen, L.A., Rhodes, E.J., 2000. Timing of Late Quaternary glaciations in the Himalayas of northern Pakistan. Journal of Quaternary Science 15, 283–297). In this paper, laboratory bleached samples from both the above studies are remeasured, using an experimental design to correct for OSL sensitivity changes, which has some similarities to the single aliquot regenerative dose (SAR) protocol of Murray and Wintle (Murray A.S., Wintle A.G., 2000. Luminescence dating of quartz using an improved single-aliquot regenerative-dose protocol. Radiation Measurements 32, 57–73). Clear evidence of thermal transfer OSL signals, generated during the preheating procedure, is presented. Further measurements, using the full SAR protocol, demonstrate that the source of this charge is related to natural dosing. For one sample, the apparent effect is subtracted effectively by the SAR protocol. Another sample studied in detail shows a striking relationship between the thermally transferred OSL signal and the total TL observed during the ramping of the preceding preheat treatment.     

Sediment dating by luminescence: a review

In the present article we review applications of luminescence methods for the determination of the age of sediments for Quaternary Earth science. “Sediment” is taken to include any mineral particles transported by wind, water and/or ice and subsequently deposited. Methodology is not discussed per se but appears in context. The emphasis is on recent work and is illustrative rather than exhaustive. Applications in archaeology are mentioned only briefly. Successful dating requires that the luminescence signal has been zeroed by sunlight at the time the sediment was laid down. Dune sands and loess transported in full daylight usually satisfy this condition and have been dated by both traditional thermoluminescence and by optical methods. Optical dating is advantageous for less well-bleached sediments, such as are found in colder climates and those laid down by fluvial and glacial processes, although the prospects for dating the latter are shown to be poor. Among less common contexts are volcanic eruptions, earthquake faults and tsunami deposits. The dating of very young sediments, less than 2 ka, is demonstrated and the factors limiting the dating of very old sediments, 500 ka to 1 Ma, are discussed. Validation of any dating method by comparison with other methods is necessary; luminescence ages have been successfully compared with ages obtained by, for example, ¹⁴C, U–Th series and δ¹⁸O isotope ratios. The most difficult problems encountered in dating quartz, feldspars and undifferentiated fine grain mixtures include: anomalous fading (which leads to underestimates of age), incomplete zeroing (which gives overestimates) and sample inhomogeneity. Methods devised to minimise these effects include preheating regimes, selection of observing wavelengths and of stimulating wavelengths for optical dating, the use of single aliquot and single grain measurements. The use of appropriate data analysis procedures is also important. Advice on current best practice on procedures for obtaining reliable ages is offered and, in all applications, there are suggestions as to where further research might be directed.     

Concepts and approaches to in situ luminescence dating of Martian sediments

In this paper we present the concept of a robotic instrument for in situ luminescence dating of near-surface sediments on Mars. The scientific objectives and advantages to be gained from the development of such an instrument are described, and the challenges presented by the Mars surface environment to the design and operation of the instrument are outlined.     

Yellow stimulated luminescence from potassium feldspar: Observations on its suitability for dating

Yellow stimulated luminescence (Y-OSL) is the light detected from potassium-rich feldspars at 410 nm under stimulation by a yellow light source emitting 590 nm. The investigation of this study aimed at understanding basic luminescence physics of Y-OSL in order to assess the suitability of the technique for dating. The Y-OSL signal properties tested were signal intensity, thermal assistance, thermal stability, sensitivity to daylight and the suitability of a single aliquot regenerative (SAR) protocol to be employed for equivalent dose (D_e) estimation. D_e measurements were conducted on samples of Holocene, last glacial and Tertiary age. The tests were undertaken on sedimentary feldspar separates extracted from aeolian, fluvial and coastal deposits.Results from experiments show that the signal intensity increases by measuring Y-OSL at elevated temperature suggesting thermal assistance characteristics similar to infrared stimulated luminescence (IRSL). The yellow stimulated signal remains unaffected by preheat temperatures up to ～200 °C suggesting higher thermal stability than the IRSL signal. The Y-OSL signal is less light sensitive than the IRSL signal and D_e residuals obtained from modern samples are up to 7 Gy indicating suitability of the technique for ‘older’ and well-bleached sediments. The dose recovery tests successfully recovered the given dose if the specific light sensitivity of Y-OSL is taken into account. For every sample Y-OSL D_e values obtained by a single aliquot regenerative dose protocol (SAR) are higher than those obtained by an IRSL SAR approach. From these results we infer high thermal stability and a minimal anomalous fading of the Y-OSL signal. We conclude that Y-OSL has a high potential to date Quaternary sediments that were sufficiently bleached in nature.     

OSL and IRSL characteristics of quartz and feldspar from southern California,USA

Southern California comprises of a wide range of diverse landscapes and environments, from high mountains with glacial and periglacial sediments to deserts with large sand dunes, extensive alluvial fans and ephemeral playas. Highly active tectonic processes has exposed ancient (c. 2 Ga) plutonic and metamorphic basement from deep within the crust, while similar Palaeozoic, Mesozoic and Cenozoic rocks are also common. A rich array of volcanic lithologies extending into the late Quaternary complement many thick sedimentary sequences that formed in equally diverse ancient environments typical of an accreting active continental margin. In some locations, notably in the Coachella Valley close to Palm Springs and the Salton Sea, low OSL sensitivity and poor characteristics restrict the application of the quartz SAR protocol to date late Pleistocene and Holocene fluvial sediments. In other locations such as the Malibu coastline, high sensitivity of the quartz OSL signal is observed, despite local source rocks being dominated by volcanic lithologies. Problems of poor quartz characteristics, along with uncertainty in predicting quartz OSL behavior for future dating campaigns poses a significant problem for projects, in particular for neotectonic contexts. While K-feldspar has been used extensively to date eolian and fluvial sediments in southern California, little information regarding signal stability is available. We explore the characteristics of both quartz and feldspar sub-samples from eolian, fluvial, lacustrine environments, in order to help develop mineral selection criteria for optical dating applications and clarify these issues. The importance of radiation quenching in quartz grains recently eroded from bedrock and the role of fires in enhancing OSL sensitivity are considered. The relative bleachability of quartz and feldspar fractions, along with thermal stability considerations is discussed. A simple test for quartz OSL signal contamination based on thermal quenching and assistance, and the susceptibility of the OSL signal to IR bleaching is introduced.     

Evidence for a weakening ‘dead zone’ in Tokyo Bay over the past 30?years

Weakened hypoxia in the past 30?years at a dredged area in Tokyo Bay was proven by the existence of amorphous hematite (α-Fe2O3) in sediments. The chemical states of iron in sediments can become a proxy for the scale of anoxia at the time of sedimentation. In 2009, we collected core sediments from a dredged area off Makuhari in Tokyo Bay that is very strongly anoxic in the summer. Every layer of the sediments was analysed by ⁵⁷Fe M?ssbauer spectroscopy and excess 210Pb dating, and amorphous hematite was identified in the sediments from the 1976–1979, 1986–1989 and 2006–2009 layers. Using an estimate based on the Eh-pH diagram optimized for the sedimental environment, the existence of hematite in the dredged area proves that the scale of hypoxia/anoxia is decreasing, and these results agree well with the observed dissolved oxygen level of the seawater mass.     

The effects of low ambient temperatures on optically stimulated luminescence (OSL) processes: Relevance to OSL dating of martian sediments

Advances in luminescence dosimetry have made geochronological dating of materials from extreme environments possible through the use of optically stimulated luminescence (OSL) single-aliquot techniques. However, these environments present challenges not always encountered in routine OSL dating, such as sediments that have been stored at low, and possibly highly variable, ambient temperatures. In recent years OSL has been proposed as a method for dating recent depositional events on surfaces of other planets, specifically, Mars. As a result it has become necessary to examine the constraints that may be imposed on the OSL method by the extreme environments of extraterrestrial planetary bodies. In this paper we report on investigations of the possible effects a low storage and/or a low OSL measurement temperature could have on the OSL process and the subsequent results. Pertinent OSL properties include the stability of electron traps, the overall luminescence efficiency, and possible thermal assistance processes. The particular focus of the work is on the potential application of the OSL technique for dating surface sediments on Mars. We report the results of OSL experiments on martian simulant materials, and of generalized computer simulations of potential OSL behavior. It is concluded that the stimulation and irradiation/calibration temperatures need to be maintained fixed throughout the experiment – i.e. the dose estimation process – and that the temperature during OSL stimulation needs to be appreciably higher than the highest temperature experienced during natural irradiation. The consequences of these findings for establishing an OSL protocol and instrument package for dating martian regolith material are discussed.     

Datierung von Ostseesedimenten mit 210Pb

The paper reports on the results of²¹⁰Pb measurement in sediment cores from the Baltic Sea. The models used for the interpretation are derived and discussed. In general, the sedimentation parameters calculated with different models are consistent. However, parameters of cores independently taken on same stations partly show clearly differing values. The reasons of this observation has to be analysed by further studies.

An essential problem considered in this paper is the dating of disturbed sediments. The use of such cores for the reconstruction of the input history of chemical indicators requires a deconvolution of data. The response function necessary for this procedure can be derived from ²¹⁰Pb measurements. The results of such a reconstruction considerably differ from those obtained by conventional dating models. The analysis of the measuring uncertainty of the indicator (e.g. lead) in the deconvolution procedure unveals the limits of the method and prevents it from overinterpretation.     

Thermal quenching of far-red Fe3+ thermoluminescence of volcanic K-feldspars

Strong thermal quenching is observed from 77 to 550 K in the far-red luminescence of K-feldspars. This far-red emission, next to the emission in the UV-to-blue spectrum recorded for thermoluminescence (TL), is reported in most alkaline feldspars with a characteristic peak centered on 710 nm with a width of 100 nm. This emission was observed by cathodoluminescence (CL) at room temperature (RT) for more than 30 K-feldspars, ranging from volcanic sanidines to granitic microclines and sediments and it is attributed to an Fe³⁺ impurity. Contrary to ‘blue’ emission in volcanic feldspars, the far-red emission displays very low anomalous fading (AF). This makes it attractive for dating purposes; however, it has weak natural TL intensity, even at saturation, which competes with the black-body emission of the heater plate. This is in contrast to an intense tunneling afterglow at liquid nitrogen temperature (LNT). Further observations show that the disadvantage of weak TL can be overcome. Photoluminescence (PL) under UV shows a very strong thermal quenching effect of the far-red emission from 77 to 550 K, which accounts for the above contrast. Near the LNT, the far-red Fe³⁺ photoluminescence is at a maximum and is dominant over other emissions in the spectrum. However, as the temperature increases, the efficiency decreases, falling to well below one percent, whereas the ‘blue’ emissions remain stable. This thermal quenching effect in photoluminescence is paralleled in TL. After irradiation and during storage at RT, whereas the ‘blue’ emission in volcanic feldspars is affected by ‘fast’ anomalous fading, charge trapped at Fe³⁺ centers as latent far-red emission is almost stable. As the TL evolves and the extant ‘blue’ emission is emitted, more and more of the trapped charge associated with far-red emission recombines non-radiatively, resulting in an efficiency for emission in natural TL that is less than one percent. A modified band model, which calls for 'hopping' conductivity during the storage, accounts for the anomalous fading. Trap emptying at lower temperatures should lead to better use of the stable latent far-red stored charge for the dating of volcanic deposits.     

Application of NAA to develop a chemostratigraphy of volcanic deposits on Nisyros and Telos, Greece

Deposits formed by explosive volcanic eruptions offer remarkable reliability when used as time-markers. Especially in time periods where radiometric dating is not applicable, sequences of volcanic layers can be used instead for relative dating. At the very least, a perfect synchronization can be established for every place where a certain volcanic layer is present. This paper deals with the development of a chronology for quaternary sediments on the island Telos. It is based upon the volcanic sequences of the islands Nisyros, Giali, and Kos. The eruptions left their traces also on the non-volcanic island Telos. During the Quaternary period, i.e., the last 1.5 million years, it has been inhabited by several groups of mammals, including elephants. These elephants underwent an outstanding dwarfing process. The time span necessary for this evolutionary process is not known and the use of the volcanic chronometer should contribute significant information to that question. Highly conveniently, at Telos itself no volcanic activity took place, but there are deposits from the eruptions mentioned above. Neutron Activation Analysis has already proven most useful for setting up an analytical database for the identification by “chemical fingerprinting” of volcanic eruption products by their element concentration patterns. A suitable number of elements, in particular As, Ba, Ce, Cr, Co, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb, Zn, Zr, is determined after one irradiation and two measurement cycles. The results show that a clear distinction between the eruption deposits of interest is possible and the sequencing of the deposits on Telos leads to the intended time scale.     

Investigation of thermoluminescence of natural zircon relevant to dating application

The thermoluminescence (TL) characteristics of natural zircons from Vietnam were studied for potential application to TL dating. All the glow curves of samples irradiated by gamma radiation or UV light showed a complex structure that consisted of a low temperature part (LTP) and a high temperature part (HTP). The TL emission spectra and monochromatic glow curves indicate that the two main impurities governing the TL emission are Dy³⁺ (LTP) and Tb³⁺ (HTP). The anomalous fading of the TL signal was assigned to the emission associated with Dy³⁺ whereas the 545 nm emission associated with Tb3⁺, exhibits significantly lower fading and consequently more suitable for TL dating.     

Experimental and computational simulation of beta-dose heterogeneity in sediment

Interpreting the spread in equivalent-dose estimates is an important aspect of optically stimulated luminescence (OSL) dating. Ideally, prior to age estimation, an assessment should be made of the likely spread in equivalent dose due to dose-rate heterogeneity in the sediment. Such a procedure would greatly increase the validity of OSL ages, particularly for sediments susceptible to partial bleaching, and for sediments with coarse or poorly sorted grain-size distributions. In this paper we take a step towards a general model of dose-rate heterogeneity by simulating the ⁴⁰K-derived beta dose to quartz. We present an experimental simulation of the ⁴⁰K beta dose, and compare the results with a Monte Carlo simulation of the same experiment. The experiment uses artificially produced ²⁴Na to simulate the ⁴⁰K beta dose to quartz, allowing a large, heterogeneous dose to be administered in a short period of time. The Monte Carlo simulation correctly predicts the shape of the equivalent-dose distribution, but underestimates the spread in dose received by different grains. The experimental set-up provides a new avenue of research into beta-dose heterogeneity.     

Radon loss from encapsulated sediments in Ge gamma-ray spectrometry for the annual radiation dose determination in luminescence dating

In Ge gamma-ray spectrometry for the annual radiation dose determination in the luminescence dating of sediments, the picture of ²²⁶Ra enrichment or depletion (in the ²³⁸U decay series) obtained via measurement of its ²¹⁴Pb and ²¹⁴Bi daughters may be disturbed by the ²²²Rn-content of the sample being decreased due to manipulations such as drying and pulverizing. Therefore, it is common practice to start the measurement only about 1 month after encapsulating the material, after which the ²²⁶Ra(1600 a)- ²²²Rn(3.82 d) mother-daughter equilibrium is re-established. Evidently, this only holds on condition that no significant escape of Rn occurs out of the sediment after making it up for counting. In order to experimentally investigate this effect, in the present work measurements were carried out with various types of dried and pulverized sediments that were either encapsulated in screw-cap polystyrene vials or in sealed glass containers, or that were mixed with molten wax followed by solidification in a cylindrical geometry. From the results obtained, it could be concluded that preparation and counting of the sediment-wax mixture is the method of choice.     

Behavioural studies of stimulated luminescence from feldspars

Since the work of Mejdahl in the mid-1980s feldspars have been used widely for palaeodosimetry. They have proved particularly popular because of the technical ease with which an optically stimulated luminescence signal can be obtained, and the potential for their use in dating over a wider time range than quartz. However, while the use of infrared stimulated lminescence has been a great success, the realisation of the potential for dating over a wide time range has been hampered by a series of behavioural problems, in particular concerned with the stability of the luminescence signal. This paper surveys the current state of knowledge of a range of aspects of the stimulated luminescence behaviour of feldspar. Particular attention is paid to the thermal and optical properties of the thermoluminescence (TL) and optically stimulated luminescence (OSL) signals from feldspars since these are of greatest relevance to their use as palaeodosimeters. Results obtained from well-characterised museum specimens demonstrate the variety of responses that are seen from different types of feldspar, particularly in their TL behaviour. Less variation is seen in their OSL response. In contrast, the response of potassium-rich feldspars separated from Quaternary sediments tends to be very consistent when many grains are analysed simultaneously, suggesting that averaging of the signal simplifies the behaviour of the system.     

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.     

Enrichment of carbon-14 by selective laser photolysis of formaldehyde

Using a frequency-doubled dye laser, simultaneous high-resolution spectra of¹⁴CH₂O and¹²CH₂O between 290 and 345 nm were measured. About 30 lines with spectral selectivities for¹⁴C≳50 were found. Photolyses on one such line at 326.94 nm of a dilute mixture of¹⁴CH₂O in natural CH₂O gave one-step enrichment factors of up to 150, with μg yields of enriched product. Since a factor of 150 in¹⁴C concentration corresponds to ∼7.2 half lives or 41,000 years, laser enrichment of archaeological samples, especially when combined with direct detection methods of¹⁴C abundance measurement, can greatly improve the range of radiocarbon dating.     

Laser enrichment of carbon-14

An experimental study has been performed of the carbon-14 enrichment achievable in the ultraviolet laser dissociation of mixtures of¹⁴CH₂O and¹²CH₂O. The¹⁴C:¹²C enrichment factor in the CO product has been measured at 352.2 nm as a function of laser linewidth, formaldehyde temperature and pressure, and degree of carbon-14 depletion. The enrichment decreases with an increase in each of these parameters; the highest enrichment, 1190, was measured at 0.02 cm^–1, 303 K, 1 Torr and a¹⁴C depletion of 10%. The results are assessed in terms of their application to radiocarbon dating, in particular for groundwater dating required for nuclear waste disposal, and to the enrichment of¹⁴C operating wastes extracted from nuclear reactors to a level suitable for commercial sale.This work was supported in part by Atomic Energy of Canada Limited     

The importance of U-series disequilibrium of sediments in luminescence dating: A case study at the Roc de Marsal Cave (Dordogne,France)

A multidisciplinary study of the Roc de Marsal Cave gave us the opportunity to re-examine the known problem posed by U-series disequilibria in sediments in the field of palaeodosimetric dating. Apart from burnt flints and heated limestones, the material being dated, THAT IS our principal concern here, is made of burnt sediment samples collected from a reddish layer that forms the very base of the Roc de Marsal Mousterian sequence (Couche B). U-series disequilibria of long life nuclides in sediments were observed: as a general trend, the activity of ²³⁸U is greater than that of ²²⁶Ra. Important discrepancies in age determination can occur according to the origin of the disequilibrium and its kinetics. To characterise these ancient modifications of radioactivity and constrain the range of possible variations of annual doses, a statistical study of ²³⁸U, ²²⁶Ra and ²³²Th activities, measured by gamma spectrometry, was carried out. It shows that the sediment was mainly enriched in mobile uranium. This conclusion is in accordance with the results of complementary measurements of ²³⁰Th and ²³⁴U performed by alpha spectrometry. On the kinetics side, two models of time-variation of U and daughter concentrations are compared, taking experimental data into account. A detailed presentation of the methodology and the method of calculation of dose rates, and particularly time-averaged dose rates in such a situation, is given.     

Mid-infrared photodetectors based on quaternary InAsSbP nanostructures

Quaternary InAsSbP quantum dots (QD) with the surface concentration of (3–5)×10⁹ cm⁻² have been grown on the InAs(100) substrate by the modified version of liquid-phase epitaxy. Morphology and distribution of densities of QDs were studied by means of atomic-force microscope. Diameter distribution of QDs was revealed to be Gaussian. The mean value of QD diameter is 23.1 nm with the variance of 6.9 nm. Two types of infrared photodetectors (IRPD) on the basis of InAs(100), with and without InAsSbP-QDs on the substrate surface, were fabricated and studied. Spectra of photoresponse of both types of IRPD at room temperature were measured and analyzed and a red shift was revealed for structures with QDs. Capacitance characteristics of IRPD and relative change in their surface resistance after irradiation with cw He-Ne laser have been studied.