Kinetic analysis of thermoluminescence glow curves in feldspar: evidence for a continuous distribution of energies

The thermoluminescence (TL) glow curves from feldspars have been the subject of numerous studies, because of their importance in luminescence dating and dosimetry. This paper presents new experimental TL glow curves in a plagioclase feldspar, measured using the T _max-T _stop technique of glow curve analysis. Kinetic analysis of the experimental results is carried out for a freshly irradiated sample, as well as for a sample which has undergone optical treatment using infrared light for 100 s at 50°C. Application of the initial rise method of analysis indicates that the TL signals from both samples can be characterized by a continuous distribution of energy levels. By subtracting the TL glow curves measured at successive T _stop values, a series of TL glow curves is obtained which are analyzed using the empirical general order kinetics. It is found that all TL glow curves obtained by this subtractive procedure can be described accurately by the same general order parameter b ～1.7. In a second attempt to analyze the same TL glow curves and possibly extract information about the underlying luminescence process, the shape of TL glow curves is analyzed using a recently proposed physical kinetic model which describes localized electronic recombination in donor-acceptor pairs. 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. This recent model has been used recently to describe successfully several types of luminescence signals. This paper shows that it is possible to obtain good fits to the experimental data using either one of these two approaches.     

Stability of IRSL signals from sedimentary K-feldspar samples

Recent work has identified IR stimulated luminescence signals at elevated temperature from both potassium- and sodium-rich feldspars that have much lower anomalous fading rates than the conventional signal measured using IR stimulation at 50°C. This paper examines the stability of these signals for potassium-rich sedimentary feldspars. We show that the natural post-IR IRSL (pIRIR) signal from a 3.6 Ma old sample is in apparent saturation on a laboratory generated dose response curve, i.e. it does not show detectable fading in nature although a low fading rate is observed on laboratory time scales. We show that the pIRIR signal has a greater thermal stability than the IRSL signal and that the trend in increasing thermal stability is mirrored by a decreasing fading rate. We also investigate the effect of preheat temperature and IR stimulation power on the decay shape and conclude that the data can be explained in terms of either a single- or multiple-trap model. We present evidence that may suggest that at least part of pIRIR signal is derived from a high temperature trap (∼550°C thermoluminescence (TL) peak), although again the data can also be explained in terms of a single-trap model. Finally, we present dose response curves and characteristic curvature constants (D₀) values for various IRSL signals and conclude that the more stable signals saturate more quickly than the less stable signals and that the initial and final signals saturate at approximately the same level.     

Firing temperature of a clay core sample in a bronze tripod from Daxinzhuang Site in China using TL techniques

In this paper, we studied the thermal history of a clay core sample from one leg of a bronze tripod unearthed at Daxinzhuang Site, Shandong, China. The properties of the luminescence signals of quartz depend on the maximum temperature at which the quartz was annealed in the past. We examined the feasibility of measuring the thermoluminescence (TL) sensitivity change of quartz for exploring the firing temperature of archaeological materials. The sensitization factor of the 110°C TL peak (S₂/S₁) and the ratio of the 210°C TL peak to the 110°C TL peak at different annealing temperatures were utilized to unveil the firing temperature in the clay core sample. The firing temperature of the clay core sample was approximately 700°C–800°C, proving the clay core has been fired. This result proved that the clay core has been fired by human agencies and indicated on the temperature of the clay core in drying and firing given by the foundry workers before the actual casting step.     

THERMOLUMINESCENCE DATING OF MATERIALS WHICH EXHIBIT ANOMALOUS FADING

This article reports a generalised and systematic approach to the thermoluminescence (TL) dating of samples which suffer from anomalous fading. We hypothesise that the TL signal from each mineral phase is composed of a stable and an unstable portion. The decay of the unstable TL is accelerated thermally, until only stable TL remains. The dating is then carried out on this stable signal. The results, on four known-age, coeval samples, exhibiting gross anomalous fading (25-50% loss over a few days), indicate that many, if not all, samples may successfully be dated with this approach.     

Luminescence dating of young coastal deposits from New Zealand using feldspar

A new measurement protocol has been tested on K-feldspars from Whanganui Inlet and Parengarenga Harbour, New Zealand. A Single Aliquot Regenerative (SAR) dose protocol, using two successive infrared (IR) stimulations (post-IR IR SAR protocol) is setup for these young (<1000 years) coastal sediments. Significant anomalous fading (g _2days =7 %/decade) is observed using the conventional IR signal measured at 50°C. In contrast, the fading rate of the IR signal measured at elevated temperature (150°C) after the IR stimulation at 50°C (a post-IR IR signal) is not significant (g _2days ≤ 1 %/decade). Surprisingly low residual infrared stimulated luminescence (IRSL) signals were observed for a surface sample, suggesting that accurate ages as young as ∼50 years can be obtained for these recent deposits. IRSL ages ranging between 48±6 years and 1050±50 years are obtained from six samples, indicating that sediment accumulation has occurred at the two sites during the last millennia, despite a falling trend in relative sea-level in Whanganui Inlet and a stable relative sea-level at Parengarenga Harbour.     

Hydrothermal palaeofluid circulation in the fracture network of the Baksa Gneiss Complex of SW Pannonian Basin,Hungary

A well‐developed fracture‐filling network is filled by dominantly Ca‐Al‐silicate minerals that can be found in the polymetamorphic rock body of the Baksa Gneiss Complex (SW Hungary). Detailed investigation of this vein network revealed a characteristic diopside→epidote→sphalerite→albite ± kfeldspar→chlorite1 ± prehnite ± adularia→chlorite2→chlorite3→pyrite→calcite1→calcite2→calcite3 fracture‐filling mineral succession. Thermobarometric calculations (two feldspar: 230–336°C; chlorites: approximately 130–300°C) indicate low‐temperature vein formation conditions. The relative succession of chlorites in the mineral sequence combined with the calculated formation temperatures reveals a cooling trend during precipitation of the different chlorite phases (T_chlorite1: 260 ± 32°C →T_chlorite2: 222 ± 20°C →T_chlorite3: 154 ± 13°C). This cooling trend can be supported by the microthermometry data of primary fluid inclusions in diopside (T_h: 276–362°C) and epidote (T_h: 181–359°C) phases. The identical chemical character (0.2–1.5 eq. wt% NaCl) of these inclusions mean that vein mineralization occurred in a same fluid environment. The high trace element content (e.g. As, Cu, Zn, Mn) and Co/Ni ratio approximately 1–5 of pyrite grains support the postmagmatic hydrothermal origin of the veins. The vein microstructure and identical fluid composition indicate that vein mineralization occurred in an interconnected fracture system where crystals grew in fluid filled cracks. Vein system formed at approximately <200 MPa pressure conditions during cooling from approximately 480°C to around 150°C. The rather different fluid characteristics (T_h: 75–124°C; 17.5–22.6 eq. wt% CaCl₂) of primary inclusions of calcite1 combining with the special δ¹⁸O signature of fluid from which this mineral phase precipitated refer to hydrological connection between the crystalline basement and the sedimentary cover.     

Comparing different post-IR IRSL approaches for the dating of Holocene coastal foredunes from Ruhnu Island,Estonia

Different post-IR Infrared Stimulated Luminescence (IRSL) approaches are applied to sediments from a Holocene coastal foredune sequence on Ruhnu Island in the eastern Baltic Sea. The comparison of D _e-values and ages determined by the different approaches is complimented by fading and bleaching experiments. The fading experiments imply strong fading of IRSL (50°C) signals and no fading of any of the post-IR IRSL signals, but this is not confirmed by the determined D _e-values. In fact, post-IR IRSL (150°C) D _e-values agree within errors with those calculated for IRSL (50°C). From the bleaching experiments it is inferred that the higher values observed for post-IR IRSL at more elevated stimulation temperatures (225°C/290°C) are likely related to either thermal transfer and/or slow-to-bleach components within the signal. For the dating of the Holocene foredune sequence of Ruhnu Island, the post-IR IRSL (150°C) approach is preferred and these agree with the limited independent age control available from radiocarbon dating. Accordingly, the sequence formed between ca. 7.0 ka and 2.5 ka ago.     

Review and assessment of the potential of post-IR IRSL dating methods to circumvent the problem of anomalous fading in feldspar luminescence

Quartz has been the main mineral used for optically stimulated luminescence (OSL) dating of sediments over the last decade. The quartz OSL signal, however, has been shown to saturate at relatively low doses of ～200–400 Gy, making it difficult to be used for dating beyond about 200 thou-sand years (ka), unless the environmental dose rate is low. The infrared stimulated luminescence (IRSL) from feldspars has been shown to continue to grow to higher dose levels than quartz OSL. The application of IRSL dating of feldspars, however, has long been hampered by the anomalous fading effect. Recent progress in understanding anomalous fading of the infrared stimulated luminescence (IRSL) signals in potassium-feldspar has led to the development of post-IR IRSL (pIRIR) protocols and also a multiple elevated temperature (MET) stimulation (MET-pIRIR) protocol. These procedures have raised the prospect of isolating a non-fading IRSL component for dating Quaternary deposits containing feldspars. In this study, we review the recent progress made on (1) overcoming anomalous fading of feldspar, and (2) the development of pIRIR dating techniques for feldspar. The potential and problems associated with these methods are discussed.     

RESEARCH REPORT: MAGNETIC INVESTIGATIONS AND THE AGE OF A MEDIEVAL KILN AT KUNGAHÄLLA (SOUTH‐WEST SWEDEN)*

The results from a magnetic survey and archaeomagnetic investigation of a medieval brick kiln at Kungahälla in Bohuslän (south‐west Sweden) are reported. Detailed magnetic total field and magnetic gradient measurements over known traces of the kiln showed marked local magnetic anomalies of up to 200 nT, revealing the rectangular shape of the kiln remains. Palaeomagnetic investigations of the remanent magnetization of 12 bricks from the kiln floor gave precise definitions of both the direction of the archaeomagnetic field [(D_m, I_m) = (66.7°, 8.8°), k = 655, α₉₅= 1.7°] and the palaeointensity [B_m= 69.0 ± 3.6 µT]. An archaeomagnetic date is obtained by comparing the direction of the archaeomagnetic field found in the kiln with a geocentral dipole‐transformation of the British master‐curve for secular variation. Of two possible archaeomagnetic dates (ad 1280 ± 50 or ad 1480 ± 50), the ad 1280 ± 50 age is in good accordance with the C‐14 ages and archaeological dates as well as with direct historical evidence, whereas a c. 100 years younger TL date appears to be too young.     

Roman traces in Germania magna: New thermoluminescence and pIRIR290 data from a lime kiln at Bergisch Gladbach,Germany

The applicability of a post‐infrared infrared stimulated luminescence (pIRIR₂₉₀) protocol and two different thermoluminescence (TL) protocols—a single aliquot regeneration (SAR) and a multiple aliquot additive dose (MAAD)—was tested on six polymineral fine‐grain (4–11 μm) samples extracted from the wall remains of a Roman lime kiln and a Roman roof tile. These remains had been excavated close to Bergisch Gladbach, which was at that time part of Germania magna. For the pIRIR₂₉₀ measurements, no dependence of D_e on first‐stimulation temperature was detectable, and the standard first stimulation temperature at 50°C was adopted. Fading tests and dose‐recovery tests were made for all samples. Background subtracted glow curves were recorded up to 480°C for TL after a preheat of 220°C for 120 s. A‐values were determined for all TL and pIRIR measurements. The results for all three protocols were fairly consistent, and TL and pIRIR₂₉₀ protocols are shown to be suitable to estimate reliable equivalent doses for the fired kiln walls. The resulting ages are in agreement with the expected time range—Roman Iron Age—and with independent age control provided by radiocarbon ages of animal bones and charcoal from the firing chamber.     

3D numerical modeling of hydrothermal processes during the lifetime of a deep geothermal reservoir

Understanding hydrothermal processes during production is critical to optimal geothermal reservoir management and sustainable utilization. This study addresses the hydrothermal (HT) processes in a geothermal research doublet consisting of the injection well E GrSk3/90 and production well Gt GrSk4/05 at the deep geothermal reservoir of Groß Schönebeck (north of Berlin, Germany) during geothermal power production. The reservoir is located between ?4050 to ?4250 m depth in the Lower Permian of the Northeast German Basin. Operational activities such as hydraulic stimulation, production (T = 150°C; Q = ?75 m³ h^?1; C = 265 g l^?1) and injection (T = 70°C; Q = 75 m³ h^?1; C = 265 g l^?1) change the HT conditions of the geothermal reservoir. The most significant changes affect temperature, mass concentration and pore pressure. These changes influence fluid density and viscosity as well as rock properties such as porosity, permeability, thermal conductivity and heat capacity. In addition, the geometry and hydraulic properties of hydraulically induced fractures vary during the lifetime of the reservoir. A three‐dimensional reservoir model was developed based on a structural geological model to simulate and understand the complex interaction of such processes. This model includes a full HT coupling of various petrophysical parameters. Specifically, temperature‐dependent thermal conductivity and heat capacity as well as the pressure‐, temperature‐ and mass concentration‐dependent fluid density and viscosity are considered. These parameters were determined by laboratory and field experiments. The effective pressure dependence of matrix permeability is less than 2.3% at our reservoir conditions and therefore can be neglected. The results of a three‐dimensional thermohaline finite‐element simulation of the life cycle performance of this geothermal well doublet indicate the beginning of thermal breakthrough after 3.6 years of utilization. This result is crucial for optimizing reservoir management. Geofluids (2010) 10 , 406–421     

Changes in natural OSL sensitivity during single aliquot regeneration procedure and their implications for equivalent dose determination

Measurement of low temperature (90°C–120°C) Thermoluminescence (TL) sensitivity of natural quartz samples subjected to pre-heating and optical stimulation indicate that significant sensitivity changes can occur during measurement of the natural Optically Stimulated Luminescence (OSL). During the measurement of natural signal, the luminescence sensitivity of samples can change by 40%. The sensitivity changes both during the initial preheat and the measurement of natural OSL. The currently used version of Single Aliquot Regeneration (SAR) protocol measures and corrects for the sensitivity changes after preheat and readout of natural OSL. However, it does not take into account the changes in sensitivity during the readout of the natural signal. We therefore developed a correction procedure so that both the natural and the regenerated OSL intensities can be measured and plotted with the same sensitivity and suggest that in the absence of such a correction, a considerable fraction of the SAR based ages could have systematic errors. The correction for the sensitivity is based on the use of sensitivity of 110°C TL quartz peak, which is correlated to OSL signal (Murray and Roberts, 1998). The use of 110°C peak provides a reasonable measure of the changes in OSL sensitivity of quartz. A modified Natural Sensitivity Corrected-SAR (NSC-SAR) procedure, that comprises the measurement of, 1) the TL intensity of 110°C peak for a test dose on sample as received (i.e. natural sample) and, 2) the sensitivity of the 110°C peak of the same sample after the preheat and read out of the natural OSL, is proposed. This ratio, termed as Natural Correction Factor (NCF), then provides a way to correct for sensitivity changes. Results on samples from diverse depositional environments indicated that the NSC-SAR consistently (without exception) provided improved distribution in paleodoses i.e. a lower scatter compared to the standard SAR protocol. In addition, the use of this protocol also resolved anomalous cases where the intensity of natural OSL was significantly above the saturation intensity of the regenerated OSL. Implicitly, this study implies a caution on the use of palaeodoses obtained from single grains as such a correction is not possible in the currently used automated single grain OSL measurement systems. The only way now on will be to analyze aliquots with only a grain on them.     

Luminescence chronology of the medieval citadel of Termez,Uzbekistan: TL dating of bricks masonries

Among the dating methods in archaeology, thermoluminescence (TL) is widely developed. The present research concerns the construction chronology of the citadel of Termez (Uzbekistan) in the medieval period. On the methodological side along the TL study, we had to take into account two decisive factors that are expected to affect the accuracy: control of anomalous fading on the polymineral fraction (quartz and feldspars) and the effect of thermal treatments on the luminescence properties of the dated material. With regard to the determination of the annual dose, difficulties, associated with the evolution of the radiochemical composition of the dated samples and their environment over time, were overcome.     

Thermospheric and mesospheric temperatures during geomagnetic storms at 23°S

Night-time thermospheric temperatures, T63o, and mesospheric rotational temperatures, T(OH) and T(O₂), have been measured at Cachoeira Paulista (23°S, 45°W, 16°S dip latitude), located in both the equatorial ionospheric anomaly and the South Atlantic Geomagnetic Anomaly, with a Fabry-Perot interferometer and a multi-channel tilting filter-type photometer, respectively. The thermospheric temperatures are obtained from the Doppler line broadening of the OI 630.0 nm emission and the mesospheric rotational temperatures from the OH(9,4) and O₂A(0,1) band emissions. Measurements made during three geomagnetic storms showed that the nocturnal mean values of T₆₃₀ during the recovery phase of the storms were lower than those observed during quiet time and from model predictions. Also, the nocturnal mean value of the T₆₃₀ soon after the SSC event on 27 June 1992 was higher than the quiet time and model predictions. The observed mesospheric nocturnal mean rotational temperatures, T(O₂) and T(O₂), were unaffected by the storms. A comparison of the night-time observed temperatures T₆₃₀, T(OH) and T(O₂) with those calculated using the MSIS-86 model is also presented.     

Electron temperature and electron density in the F-region of the ionosphere. I. Observed relationship

Ionospheric data from three incoherent scatter stations over the height range 225–450 km were studied for all daylight hours over a wide range of solar conditions. The relationship between electron temperature T_e, electron density Nand solar flux at 10.7 cm wavelength S_10.7 was expressed as T_e = A−B·(N−5 × 10¹¹) + C·(S_10.7−750), where N is in units of m⁻³ and S_10.7 in kJy.This provided a very satisfactory expression for all data taken at Malvern and St. Santin between 0800 and 1600 LT. For data taken at Arecibo, however, the linearity broke down at low electron densities. The data from all three stations were therefore divided into two sets according to electron density and reexamined.ForN < 5 × 10¹¹ m⁻³ B increased steadily with height and decreased steadily with latitude.For N > 5 × 10¹¹ m⁻³ B did not appear to vary with height, with season or with latitude. C was approximately constant for all sets of data.The different mechanisms involved in the heat balance of the electron population are discussed and a qualitative explanation for the relationship is proposed.     

The effect of the mid-latitude ionospheric trough on whistler mode ducting during magnetic storms

Whistler-mode signals observed at Faraday, Antarctica (65° S, 64° W, Λ=50.8°) show anomalous changes in group delay and Doppler shift with time during the main phase of intense geomagnetic activity. These changes are interpreted as the effect of refracting signals into and out of ducts near L=2.5 by electron concentration gradients associated with edges of the mid-latitude ionospheric trough. The refraction region is observed to propagate equatorwards at velocities in the range 20–85 ms⁻¹ during periods of high geomagnetic activity (K_p ≥ 5), which is in good agreement with typical trough velocities. Model estimates of the time that the trough edges come into view from Faraday show a good correlation with the observed start times of the anomalous features. Whistler-mode signals observed at Dunedin, New Zealand (46° S, 171° E, Λ=52.5°) that have propagated at an average L-shell of 2.2 (Λ=47.6°) do not show such trough-related changes in group delay. These observations are consistent with a lower occurrence of the trough at lower invariant latitudes.     

The D e (T,t) plot: A straightforward self-diagnose tool for post-IR IRSL dating procedures

This study presents a new self-diagnose method for the recently developed post-IR infrared stimulated luminescence (pIRIR) dating protocols. This criterion studies the dependence of equivalent dose (D _e) on measurement-temperature (T) and time (t), by applying the D _e (t) analysis to the IRLS and pIRIR signals measured under different temperatures, and combines these D _e (t) plots into one, so-called the D _e (T, t) plot. The pattern of the D _e (T, t) plot is shown to be affected by anomalous fading, partial bleaching and non-bleachable signal. A D _e plateau can be achieved in the D _e (T, t) plot only when the effects of these factors are insignificant. Therefore, this plot can be used as a self-diagnose tool for the validity of pIRIR results. The D _e (T, t) analysis has been applied to four recently developed pIRIR protocols, using aeolian samples with different ages. The results show that this self-diagnose tool can be applied to different pIRIR protocols for validating the pIRIR dating results and evaluating the pIRIR measurement conditions.     

Molecular transport of methane, ethane and nitrogen and the influence of diffusion on the chemical and isotopic composition of natural gas accumulations

Laboratory experiments have been performed to determine diffusion coefficients of natural gas components (methane, ethane and nitrogen) and isotope fractionation effects under simulated in situ pressure (up to 45 MPa effective stress) and temperature conditions (50–200°C) in water‐saturated pelitic and coarse‐grained rocks. Effective diffusion coefficients of molecular nitrogen (0.39 × 10^?11 to 21.6 × 10^?11 m² sec^?1 at 90°C) are higher than those for methane (0.18 × 10^?11 to 18.2 × 10^?11 m² sec^?1 at 90°C). Diffusive flux rates expressed in mass units are generally higher for N₂ than for CH₄. Both methane and (to a lesser extent) nitrogen diffusion coefficients decrease with increasing total organic carbon (TOC) content of the rock samples because of sorption processes on the organic matter. This effect decreases with increasing temperature. Effective diffusion coefficients increase upon a temperature increase from 50 to 200°C by a factor of four. Effective diffusion coefficients and steady‐state diffusive flux decrease with effective stress. Stationary diffusive fluxes drop by 50–70% for methane and 45–62% for nitrogen while effective diffusion coefficients are reduced by 38% (CH₄) and 32–48% (N₂), respectively. Isotope fractionation coefficients of diffusive transport are higher for methane (?1.56 and ?2.77‰) than for ethane (?0.84 and ?1.62‰). Application of the experimental results to geological systems show that diffusive transport has only a low transport efficiency. Significant depletion of natural gas reservoirs by molecular diffusion is only expected in cases of very poor caprock qualities (in terms of thickness and/or porosity) and over extended periods of geological time. Under these circumstances, the chemical and isotopic composition of a gas reservoir will change and maturity estimates based on these parameters may be deceptive. To account for these potential effects, nomograms have been developed to estimate diffusive losses and apply maturity corrections.     

PROGRESS IN TL DATING AT RISÖ

This article outlines the thermoluminescent dating technique employed at Risö. The intensity of beta and gamma radiation is determined by means of the TL phosphors CaSO₄:Mn and CaSO₄:Dy, and the determination of accumulated exposure is based on quartz and feldspar inclusions with a size of 0.3–0.5 mm. Results are presented of a dating programme comprising sherds, bricks, burned stones and burned clay (from kilns) from seventeen excavation sites. The age of the sites ranged from a.d. 1600 to 4000 b.c.     

High‐temperature magmatic fluid exsolved from magma at the Duobuza porphyry copper–gold deposit,Northern Tibet

The Duobuza porphyry copper–gold deposit (proven Cu resources of 2.7 Mt, 0.94% Cu and 13 t gold, 0.21 g t^?1 Au) is located at the northern margin of the Bangong‐Nujiang suture zone separating the Qiangtang and Lhasa Terranes. The major ore‐bearing porphyry consists of granodiorite. The alteration zone extends from silicification and potassic alteration close to the porphyry stock to moderate argillic alteration and propylitization further out. Phyllic alteration is not well developed. Sericite‐quartz veins only occur locally. High‐temperature, high‐salinity fluid inclusions were observed in quartz phenocrysts and various quartz veins. These fluid inclusions are characterized by sylvite dissolution between 180 and 360°C and halite dissolution between 240 and 540°C, followed by homogenization through vapor disappearance between 620 and 960°C. Daughter minerals were identified by SEM as chalcopyrite, halite, sylvite, rutile, K–feldspar, and Fe–Mn‐chloride. They indicate that the fluid is rich in ore‐forming elements and of high oxidation state. The fluid belongs to a complex hydrothermal system containing H₂O – NaCl – KCl ± FeCl₂ ± CaCl₂ ± MnCl₂. With decreasing homogenization temperature, the fluid salinity tends to increase from 34 to 82 wt% NaCl equiv., possibly suggesting a pressure or Cl/H₂O increase in the original magma. No coexisting vapor‐rich fluid inclusions with similar homogenization temperatures were found, so the brines are interpreted to have formed by direct exsolution from magma rather than trough boiling off of a low‐salinity vapor. Estimated minimum pressure of 160 MPa imply approximately 7‐km depth. This indicates that the deposit represents an orthomagmatic end member of the porphyry copper deposit continuum. Two key factors are proposed for the fluid evolution responsible for the large size of the gold‐rich porphyry copper deposit of Duobuza: (i) ore‐forming fluids separated early from the magma, and (ii) the hydrothermal fluid system was of magmatic origin and highly oxidized.