The luminescence decay-time of Mn2+ activated calcite

Luminescence decay time data are presented for 17 samples of synthetic calcite and a natural calcite between room temperature and approximately 15 K. The majority of the samples have Mn concentration in the range 0.0001–0.01 atoms per formula unit (apfu). Their spectra are consistent with a single exponential decay. It was necessary to use a “stretched” exponential to obtain adequate fits to the spectra of two samples having Mn concentrations of 0.036 and 0.091 apfu. The decay time at room temperature ranges from approximately 40–57 ms. At low temperature the corresponding range is 51–120 ms, indicating that thermal quenching of the decay time takes place. The decay time is dependent on the concentration of Mn, reaching a maximum (at both room- and low-temperature) in the range 0.001–0.003 apfu. The composition dependence is greater at low temperature. The results are discussed in terms of the Mott-Seitz and multiphonon mechanisms of thermal quenching. It is concluded that the latter provides a better fit to the data and is more consistent with models of the luminescence process in calcite:Mn.     

Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

The nature of blue luminescence from natural benitoite BaTiSi<Subscript>3</Subscript>O<Subscript>9</Subscript>

It is proved that blue luminescence from benitoite is connected with intrinsic luminescence centers, namely isolated TiO₆ octahedra. The metastable level ³T_1u is the emitting level at low temperatures with a long decay time of 1.1 ms. At higher temperatures an energy level with higher radiation probability must be involved in the emission process, and this level is situated at 0.06 eV higher than the lowest level. These two levels may be connected with ³T_1u level splitting or with closely spaced ³T_1u and ³T_2u levels. Decay time shortening and thermal quenching are connected with nonradiative decay within the TiO₆ luminescence center, while energy migration does not take place at least up to room temperature.     

Photoluminescence properties of thenardite from Ai-Ding Salt Lake,Xinjiang, China

The photoluminescence (PL) spectra, excitation spectra, and PL decay curves of natural, heat-treated, and γ-ray-irradiated thenardites from Ai-Ding Salt Lake, Xinjiang, China, were studied. The natural thenardite under 300 nm excitation showed milk-white luminescence, and the PL spectrum consisted of an extremely broad band with a peak located at approximately 509 nm, spreading over a wide range of UV and visible wavelengths. The excitation spectra, obtained by monitoring the luminescence at 530 nm, consisted of a broad band with a peak located at approximately 235 nm and a flat band spreading over a wide range of UV and visible wavelengths. The PL decay curve of natural thenardite consisted of a fast-decay component with a lifetime of less than 0.1 μs and a slow-decay component with a half-decay time of approximately 0.4 s. The heat treatment of thenardite at 900°C for 20 min reduced the luminescence efficiency to 1/100. The γ-ray irradiation of thenardite reduced the luminescence efficiency to approximately half.     

Photoluminescence properties of anthophyllite

The photoluminescence (PL) spectra, optical excitation spectra and PL decay curves of anthophyllite from Canada were obtained at 300 and 10 K. The MnO content in the sample, determined using an electron probe microanalyzer, was high at 5.77 wt%. In the PL spectra obtained under 410-nm excitation, bright red bands with peaks at 651 and 659 nm were observed at 300 and 10 K, respectively. The origin of the red luminescence was ascribed to Mn²⁺ in anthophyllite from the analysis of the excitation spectra and PL decay times of 6.1–6.6 ms. In the PL spectra obtained under 240-nm excitation at 300 K, a small violet band with a peak at 398 nm was observed. On the violet band at 10 K, a vibronic structure was observed. The origin of the violet luminescence was attributed to a minor impurity in anthophyllite.     

Photoluminescence of baratovite and katayamalite

The photoluminescence (PL) and optical excitation spectra of baratovite in aegirine syenite from Dara-i-Pioz, Tien Shan Mts., Tajikistan and katayamalite in aegirine syenite from Iwagi Islet, Ehime, Japan were obtained at 300 and 80 K. Under short wave (253.7 nm) ultraviolet light, baratovite and katayamalite exhibited bright blue-white luminescence. The PL spectrum of baratovite at 300 K consisted of a wide band with a peak at approximately 406 nm and a full width at half maximum (FWHM) of approximately 6.32k cm⁻¹. The excitation spectrum of the blue-white luminescence from baratovite at 300 K consisted of a prominent band with a peak at approximately 250 nm. The PL and excitation spectra of katayamalite were similar to those of baratovite. The luminescence from these minerals was attributed to the intrinsic luminescence from the TiO₆ center.     

Photoluminescence properties of green and red luminescence from natural and heat-treated sodalite

The sodalite sample used in this investigation did not exhibit the characteristic orange-yellow luminescence due to the $ {\text{S}}_{ 2}^{ - } $ center, because there was no trace of sulfur impurity. The heat-treated samples exhibited green and red luminescence with maximum intensity at 496 and 687 nm, respectively, under 264 nm excitation at room temperature. Their luminescence intensities were extensively dependent on the treatment temperature. The green luminescence efficiency of the sample heat-treated at 900 °C was 6.5 times higher than that of unheated natural sodalite. At 8.5 K, the green luminescence showed a vibronic structure. After heating at 1,300 °C, the crystal structure of sodalite was transformed to NaAlSiO₄ (carnegieite), and the intense red luminescence was exhibited in the NaAlSiO₄ sample. The peak wavelength of the red luminescence shifted from 687 nm at 300 K to 726 nm at 8.5 K. The luminescence lifetimes of the green and red luminescence at room temperature were 2.1 and 5.1 ms, respectively. It was proposed that the origin of the green luminescence is Mn²⁺ replacing Na⁺, and that of the red luminescence is Fe³⁺ replacing Al³⁺ in sodalite or NaAlSiO₄ (carnegieite).     

Mesozoic thermal history of the Prebetic continental margin (southern Spain): Constraints from apatite fission-track analysis

Apatite fission-track analysis was applied to Triassic and Cretaceous sediments from the South-Iberian Continental Margin to unravel its thermal history. Apatite fission-track age populations from Triassic samples indicate partial annealing and point to a maximum temperature of around 100–110 °C during their post-depositional evolution. In certain apatites from Cretaceous samples, two different fission-track age populations of 93–99 and around 180 Ma can be distinguished. Track lengths associated with these two populations enabled thermal modelling based on experimental annealing and mathematical algorithms. These thermal models indicate that the post-depositional thermal evolution attained temperatures ≤ 70 °C, which is consistent with available vitrinite-reflectance data. Thermal modelling for the Cretaceous samples makes it possible to decipher a succession of cooling and heating periods, consisting of (a) a late Carboniferous–Permian cooling followed by (b) a progressive heating episode that ended approximately 120 Ma at a maximum T of around 110 °C. The first cooling episode resulted from a combination of factors such as: the relaxation of the thermal anomaly related to the termination of the Hercynian cycle; the progressive exhumation of the Hercynian basement and the thermal subsidence related to the rifting of the Bay of Biscay, reactivated during the Late Permian. Jurassic thermal evolution deduced from the inherited thermal signal in the Cretaceous sediments is characterized by progressive heating that ended around 120 Ma. This heating episode is related to thermal subsidence during Jurassic rifting, in agreement with the presence of abundant mantle-derived tholeiitic magmas interbedded in the Jurassic rocks. The end of the Jurassic rifting is well marked by a cooling episode apparently starting during Neocomiam times and ending at surface conditions by Albian times.     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Heat-induced changes in speciation and extraction of uranium associated with sheet silicate minerals

Three samples of gouge from a U-mineralised fault, and two model samples, montmorillonite and muscovite, spiked with U, were heat-treated at a range of temperatures up to 1100 °C. Mineralogical changes were followed by thermal analysis, powder XRD and electron microscopy, and U extractability was measured by extraction with NH₄⁺. Changes in U speciation in the montmorillonite sample were followed using EXAFS spectroscopy. On heating, the minerals progressively dehydrate, dehydroxylate and eventually decompose to form new phases in a glassy matrix. In the case of montmorillonite (90% of U extractable from unheated material), U extractability increased slightly on heating to temperatures around 400 °C. Almost 50% of U was extracted from unheated muscovite, and this increased slightly by 450 °C. Above 500–600 °C, U extractability from both montmorillonite and muscovite declined to very low levels, reflecting dehydration of the uranyl ion and trapping in the new phases and glassy matrix. Uranium extractability from the natural samples was much lower in all cases (0.25–5% of the total before heating). In 2 samples, a significant increase in U extraction was associated with dehydroxylation at around 600 °C, followed by a decrease to very low levels at higher temperatures. Uranium extraction from the third natural sample, which contained X-ray amorphous U minerals, decreased steadily on heating. The results show that changes in U extraction can be related to structural and morphological changes in sheet silicate minerals. Heat treatment has potential to fix U but only if temperatures above 800 °C are reached. If only lower temperatures, in the range 400–600 °C, are used, then U extraction may increase.     

Linear relationship between thermo-dehydroxylation and induced-strain by mechanical processing in vacuum: The case of industrial kaolinite, talc and montmorillonite

The thermal behaviour and the structural properties of three important industrial phyllosilicates, such as kaolinite, talc and Ca-rich montmorillonite, have been examined after mechanical treatment in a specifically built planetary ball mill working in vacuum (P = 0.13 Pa) at room temperature (25 °C). It is found that, on increasing the grinding time, the temperature of the dehydroxylation reaction decreases linearly as a result of a decrease of the crystallite size and structural order. To be noted that the mechanical treatment in our milling conditions did not induce significant amorphization. The temperature at which there is the maximum of dehydroxylation and the weight losses of the intralayer OH are linearly related to the increase of the FWHM of the 001 basal plane. These results are useful for predicting the thermal behaviour of layer silicates to be subjected to mechanical processing in industrial application.     

OH in natural orthopyroxene: an in situ FTIR investigation at varying temperatures

In situ unpolarized and polarized Fourier transform infrared spectra of a natural orthopyroxene at varying temperatures were obtained using a heating stage attached on an Infrared microscope. The three main bands (3,595, 3,520 and 3,410 cm⁻¹) at room temperature are ascribed to OH fundamental stretching bands. With increasing temperature from room temperature to 500 °C, the 3,595 cm⁻¹ band shifts 20 cm⁻¹ to lower frequency. The total integral absorbance decreases with increasing temperature. These changes are reversible. Excluding the influences of dehydration, proton migration, thermal expansion, and changes in OH dipole direction, the change of integral absorbance with temperature reflects the temperature dependence of absorption coefficient due to the anharmonicity of OH vibration. Based on the integral absorption coefficient at room temperature (14.84 ppm⁻¹ cm⁻²) from Bell et al. (Am Mineral 80:463–474, 1995), the integral absorption coefficients at other temperatures are calculated. The variation of integral absorption coefficient between room temperature and 500 °C obtained in this study is about 18.5 % and may be greater at higher temperature according to the proposed linear relationship.     

A review of the thermal regime of the Eastern Alps with respect to the effects of paleoclimate and exhumation

Transient thermal signals such as Pleistocene surface temperature variations or exhumation of great rock volumes are important for the current thermal regime of the Eastern Alpine crust. In this study transient 1-D forward simulations and an analytical approach were used to estimate the order of magnitude of these effects. A comparison with numerical forward simulations and inverse analyses of steady-state heat conduction yields the following main conclusions with respect to the thermal regime of the Eastern Alps along the TRANSALP profile: (1) The change of surface temperatures in the past affects mainly the uppermost part of the Eastern Alpine crust. It results in a maximum thermal signature of more than − 6 K at a depth of 2 km. The deviations from a steady-state temperature gradient and heat flow in the region of the Tauern Window range from 0.3–4 K km^− 1 and 0–6 mW m^− 2, respectively, with maximum values at the surface. (2) Exhumation of the Eastern Alpine lithosphere may result in a thermal signature of up to 4 K at a depth of 1 km. The thermal signature increases further with depth to a maximum of approximately 80 K at a depth of 50 km. As the temperature gradient of the exhumation signal is almost zero at the base of the crust, Moho heat flow appears to be not critically perturbed. (3) The combined effect of exhumation and changing surface temperatures at the Tauern Window amounts to less than 15% of the steady-state temperatures at a depth of  8 km and to less than 10% at the base of Eastern Alpine root. The corresponding perturbation in heat flow is less than 20% at a depth of 4 km, approaching zero below 40 km.     

Laboratory testing and numerical simulation of properties and thermal-induced cracking of Eibenstock granite at elevated temperatures

The knowledge about thermo-mechanical properties of granite is still limited to some extent. Individual measurements are necessary to obtain reliable properties for specific granite types. A reliable numerical model of thermal cracking behaviours of granite exposed to extreme high temperatures (e.g. 800–1000 °C) is missing. In this study, the impact of temperature up to 1000 °C on physical, mechanical, and thermal properties as well as thermo-mechanical coupled behaviour of Eibenstock granite was investigated by laboratory testing and numerical simulations. The physical properties including mineral composition, density, P-wave velocity, and open porosity are measured to be temperature dependent. Uniaxial compression and Brazilian tests were carried out to measure uniaxial compressive strength (UCS), Young’s modulus, stress–strain relationship, and tensile strength of Eibenstock granite before and after thermal treatment, respectively. Thermal properties including specific heat, thermal conductivity, thermal diffusivity, and linear thermal expansion coefficient are also measured and found to be temperature dependent, especially the expansion coefficient which shows a steep increase around 573 °C as well as at 870 °C. The numerical simulation code FLAC^3D was used to develop a numerical scheme to simulate the thermal-induced damage of granite at high temperatures. Statistical methods combined with real mineral composition were used to characterize the heterogeneity of granite. The numerical model is featured with reliable temperature-dependent parameters obtained from laboratory tests. It can well reproduce the laboratory results in form of thermal-induced micro- and macrocracks, as well as the stress–strain behaviour and the final failure pattern of Eibenstock granite after elevated temperatures up to 1000 °C. The simulation results also reveal that the thermal-induced microcracks are randomly distributed across the whole sample. Although most thermal-induced damages are tensile failures, shear failure begins to develop quickly after 500 °C. The obvious UCS reduction in granite due to heating is mainly caused by the increase in shear failure. The simulation also shows that the dominant impact of α–β quartz transition is widening pre-existing cracks rather than the formation of new microcracks.

     

Photoluminescence spectra of S<Subscript>2</Subscript><Superscript><Emphasis Type="Bold">−</Emphasis></Superscript> center in natural and heat-treated scapolites

The emission and excitation spectra of yellow luminescence due to S₂ ⁻ in scapolites (#1 from Canada and #2 from an unknown locality) were observed at 300, 80 and 10 K. Emission and excitation bands at 10 K showed vibronic structures with a series of maxima spaced 15–30 and 5–9 nm, respectively. The relative efficiency of yellow luminescence from scapolite #2 was increased up to 117 times by heat treatment at 1,000°C for 2 h in air. The enhancement of yellow luminescence by heat treatment was ascribed to the alteration of SO₃ ²⁻ and SO₄ ²⁻ to S₂ ⁻ in scapolite.     

Temperature dependence on the electron paramagnetic resonance spectra of natural jasper from Taroko Gorge (Taiwan)

Structural properties of natural jasper from Taroko Gorge (Taiwan) have been investigated by means of powder X-ray diffraction, electron paramagnetic resonance (EPR) and Fourier transform infrared spectroscopic techniques. The EPR spectrum at room temperature exhibits a sharp resonance signal at g = 2.007 and two more resonance signals centered at g ≈ 4.3 and 14.0. The resonance signal at g = 2.007 has been attributed to the E′ center and is related to a natural radiation-induced paramagnetic defect. Two more resonance signals centered at g ≈ 4.3 and 14.0 are characteristic of Fe³⁺ ions. The EPR spectra recorded at room temperature of jasper samples, heat-treated at temperatures ranging from 473 to 1,473 K exhibit marked temperature dependence. The resonance signal corresponding to E′ center disappears at elevated temperatures. A broad, intense resonance signal centered at g ≈ 2.0 appears at elevated temperatures. This resonance signal is a characteristic of Fe³⁺ ions, which are present as hematite in the jasper sample. The intensity of the resonance signal becomes dominant at elevated temperatures at ≥873 K, masking g ≈ 4.3 and g ≈ 14.0 resonance signals. The EPR spectra of jasper heat-treated at 673 K have been recorded at temperatures between 123 and 296 K. The population of spin levels (N) has been calculated for the broad g ≈ 2.0 resonance signal. It is found that N decreases with decreasing temperature. The linewidth (ΔH) of g ≈ 2.0 resonance signal of the heat-treated jasper is found to increase with decreasing temperature. This has been attributed to spin–spin interaction of the Fe³⁺ ions present in the form of hematite in the studied jasper sample.     

Influence of shear heating on microstructurally defined plate boundary shear zones

In plate-boundary scale ductile shear zones defined by microstructural weakening, shear heating may lead to a temperature increase over 5 m.y. of up to 80 °C just below the brittle ductile transition, up to 120 °C just below the Moho, and to thermal boundary zones tens of km wide on either side of the shear zone. Where rock strength is highest, shear zones are narrow (∼1 km), and thermal gradients within the shear zone itself are low, so there is no tendency for increased localization. Heating results in thermal weakening, but this is partly offset by grain growth related to the decrease in stress. In shear zones of the order of 10 km width, shear stress, strain rate, and hence heat generation are lower, and thermal gradients are insufficient to cause additional strain localization. Temperature increases in the mid-crust are of the order of 10 °C, insufficient to cause partial melting or an increase in metamorphic grade. In the upper mantle, shear zones may be 50 km or more wide, and the temperature increase is less than 20 °C in 5 m.y., but temperature differences between center and margin may enhance the strain rate at the center by up to 18%.     

The luminescence dating chronology of a deep core from Bosten Lake (NW China) in arid central Asia reveals lake evolution over the last 220 ka

The lacustrine deposits of lakes in arid central Asia (ACA) potentially record palaeoclimatic changes on orbital and suborbital time scales, but such changes are still poorly understood due to the lack of reliable chronologies. Bosten Lake, the largest freshwater inland lake in China, is located in the southern Tianshan Mountains in central ACA. A 51.6‐m‐deep lacustrine succession was retrieved from the lake and 30 samples from the succession were used for luminescence dating to establish a chronology based on multi‐grain quartz OSL and K‐feldspar post‐IR IRSL (pIRIR₂₉₀) dating. Quartz OSL ages were only used for samples from the upper part of the core. The K‐feldspar luminescence characteristics (dose recovery test, anomalous fading test, first IR stimulation temperature plateau test) are satisfactory and from the relationship amongst the quartz OSL, IR₅₀ and pIRIR₂₉₀ doses we infer that the feldspar signals are likely to be well bleached at deposition. Bacon age‐depth modelling was used to derive a chronology spanning the last c. 220 ka. The chronology, lithology and grain‐size proxy record indicate that Bosten Lake formed at least c. 220 ka ago and that lake levels fluctuated frequently thereafter. A stable deep lake occurred at c. 220, 210–180, c. 165, 70–60, 40–30 and 20–5 ka, while shallow levels occurred at c. 215, 180–165, 100–70, 60–40 and 30–20 ka. Bosten Lake levels decreased by at least ~29 m and possibly the lake even dried up between c. 160 and c. 100 ka. We suggest that the water‐level fluctuations in the lakes of ACA may not respond directly to climatic changes and may be affected by a number of complex factors.     

Ultraviolet-blue ionic luminescence of alkali feldspars from bulk and interfaces

Laboratory driven ionic thermal exchange of alkali feldspars from K to Na produces samples which are strongly luminescent in the ultraviolet region near 320 nm. The sites providing this luminescence are suggested as being correlated with the motion of Na atoms along interface-interphases of the material (i.e. with Na-O bond fracture). The thermoluminescence peaks show multi-order kinetics. Thermal preheatings of low albite sensitize the feldspar lattice with respect to thermoluminescence generated by exposure to UV irradiation and heating produces a strong blue luminescence spread over the range 350 nm to 500 nm band in feldspars. The upper temperature for thermoluminescence in feldspars is ∼300 °C, which is also the point where ionic conductivity of albite (010) begins, but the 300 °C region is also the starting point of a large second glow peak in adularia. Whilst it seems appropriate to link the Na motion to the 350–500 nm emission, it is unclear whether these changes are the result of the large anisotropic thermal vibration of Na atoms or the massive Na jumps that occur when the lattice reaches 300 °C. A speculative model is considered in which the UV TL emissions of natural minerals are linked to different interface-interphases (grain boundaries, exsolution limits, twinning planes, antiphase domains). Increased interface coherency energies are related to the kinetic order and the spectral position of luminescence emission peaks. Received: 3 December 1998 / Revised, accepted: 17 April 1999     

Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study

The structure of deuterated jarosite, KFe₃(SO₄)₂(OD)₆, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH)₆] octahedra and [SO₄] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, α = α₀ + α₁ T, where α₀ = 1.01 × 10⁻⁴ K⁻¹ and α₁ = −1.15 × 10⁻⁷ K⁻². On heating, the hydrogen bonds, O1···D–O3, through which the (001) octahedral–tetrahedral sheets are held together, become weakened, as reflected by an increase in the D···O1 distance and a concomitant decrease in the O3–D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.