Point defects and pre-dose requirements for sensitization of the 300°C TL peak in natural quartz

This paper discusses the structural features required to stimulate a strong thermoluminescence (TL) glow peak near 300°C in clear natural quartz. For that reason, fresh TL data taken from several specimens prepared from five single crystals with known impurity content are shown. The TL emission was measured with a test dose of 10 mGy of γ-rays in the readout intervals 50–160 and 160–320°C. The readings were carried out prior and after the administration of a pre-dose of 175 kGy of γ-rays followed by heat-treatments at 400°C. For each single specimen, the OH content and the population of inclusions were evaluated by infrared spectroscopy and optical microscopy, respectively. The darkening induced by high γ dose was evaluated by optical spectroscopy. It was observed that the absorption at 475 nm and TL responses decrease with increase of the OH. It was shown that both smoky darkening and TL signals were better explained in terms of Li/Al and Li/OH content ratios rather than the absolute values of aluminum and alkali concentrations. The sensitization with high γ dose and heating is essential to create and stabilize a class of defects sites with Li⁺ ions dislodged from [AlO₄/Li]⁰ and Li-dependent OH centers. It is suggested that the defect sites formed with Li⁺ act as electron traps during test dose irradiation, whereas electron-hole recombination occurs essentially at [AlO₄]⁰ centers during the TL output near 300°C.     

Correlation between electron paramagnetic resonance and thermoluminescence in natural sodalite

Samples of natural sodalite, Na₈Al₆Si₆O₂₄Cl₂, submitted to gamma irradiation and to thermal treatments, have been investigated using the thermoluminescence (TL) and electron paramagnetic resonance (EPR) techniques. Both, natural and heat-treated samples at 500°C in air for 30 min, present an EPR signal around g = 2.01132 attributed to oxygen hole centers. The EPR spectra of irradiated samples show an intense line at g = 2.0008 superimposed by a hyperfine multiplet of 11 lines due to an O⁻ ion in an intermediate position with respect to two adjacent Al nuclei. In the TL measurements, the samples were annealed at 500°C for 30 min and then irradiated with γ doses varying from 0.001 to 20 kGy. All the samples have shown TL peaks at 110, 230, 270, 365, and 445°C. A correlation between the EPR g = 2.01132 line and the 365°C TL peak was observed. A TL model is proposed in which a Na⁺ ion acts as a charge compensator when an Al³⁺ ion replaces a Si⁴⁺ lattice ion. The γ ray destruction of the Al–Na complex provides an electron trapped at the Na and a hole trapped at a non-bridging oxygen ion adjacent to the Al³⁺ ion.     

Thermoluminescence, electron paramagnetic resonance and optical absorption in natural and synthetic rhodonite crystals

Thermoluminescence, electron paramagnetic resonance and optical absorption properties of rhodonite, a natural silicate mineral, have been investigated and compared to those of synthetic crystal, pure and doped. The TL peaks grow linearly for radiation dose up to 4 kGy, and then saturate. In all the synthetic samples, 140 and 340°C TL peaks are observed; the difference occurs in their relative intensities, but only 340°C peak grows strongly for high doses. Al₂O₃ and Al₂O₃ + CaO-doped synthetic samples presented several decades intenser TL compared to that of synthetic samples doped with other impurities. A heating rate of 4°C/s has been used in all the TL readings. The EPR spectrum of natural rhodonite mineral has only one huge signal around g = 2.0 with width extending from 1,000 to 6,000 G. This is due to Mn dipolar interaction, a fact proved by numerical calculation based on Van Vleck dipolar broadening expression. The optical absorption spectrum is rich in absorption bands in near-UV, visible and near-IR intervals. Several bands in the region from 540 to 340 nm are interpreted as being due to Mn³⁺ in distorted octahedral environment. A broad and intense band around 1,040 nm is due to Fe²⁺. It decays under heating up to 900°C. At this temperature it is reduced by 80% of its original intensity. The pink, natural rhodonite, heated in air starts becoming black at approximately 600°C.     

Chemical and physical studies of type 3 chondrites—IV: Annealing studies of a type 3.4 ordinary chondrite and the metamorphic history of meteorites

Samples of a type 3.4 chondrite have been annealed at 400–1000°C for 1–200 hours, their thermoluminescence properties determined and analyzed for K, Na, Mn, Sc and Ca by instrumental neutron activation analysis. After annealing at ?900°C, the samples showed a 50% decrease in TL sensitivity, while after annealing at 1000°C it fell to 0.1-0.01 times its unannealed value and loss of Na and K occurred. The TL and compositional changes resemble those observed for the equilibrated Kernouve chondrite after similar annealing treatments, except that the sharp TL decrease, and element loss, occurred at ~ 1100°C; this difference is presumably due to petrographic differences in the feldspar of the two meteorites. The temperature and the width of the TL peak showed a discontinuous increase after annealing at 800°C; peak temperature jumped from 130 to 200°C and peak width increased from 90 to 150°C. The activation energies for these TL changes are 7–10 kcal/mole. Similar increases in the TL peak temperature have been reported in TL studies of Amelia, VA, albite, where they were associated with the low to high-temperature transformation. However, the activation energy for the transformation is ~80 kcal/mole. These changes in TL emission characteristics resemble trends observed in type 3 ordinary chondrites and it is suggested that type 3.3–3.5 chondrites have a low-feldspar as TL phosphor and > 3.5 have high-feldspar as the phosphor. Thermoluminescence therefore provides a means of palaeothermometry for type 3 ordinary chondrites.     

Chemical and physical studies of type 3 chondrites—VIII: Thermoluminescence and metamorphism in the CO chondrites

The thermoluminescence properties of nine CO chondrites have been measured. With the exception of Colony and Allan Hills A77307 (ALHA 77307), whose maximum induced TL emission is at approximately 350°C, CO chondrites exhibit two TL peaks, one at 124 ± 7°C (130°C peak) and one at 252 ± 7°C (250°C peak). The 130°C peak shows a 100-fold range in TL sensitivity (0.99 ± 0.21 for Isna to 0.010 ± 0.004 for Colony), and correlates with various metamorphism-related phenomena, such as silicate heterogeneity, metal composition and McSween's metamorphic subtypes. The peak at 250°C does not show these correlations and, Colony excepted, varies little throughout the class (0.3 to 0.07, Colony 0.018 ± 0.004). Mineral separation experiments, and a series of annealing experiments on Isna, suggest that the TL properties for CO chondrites reflect the presence of feldspar in two forms, (1) a form produced during metamorphism, and analogous to the dominant form of feldspar in type 3 ordinary chondrites, and (2) a primary, metamorphism-independent form, perhaps associated with the amoeboid inclusions. If this interpretation is correct, then the CO chondrites have not experienced temperatures above the order/disorder temperature for feldspar (500–600°C) and they cooled more slowly than comparable (i.e. type <3.5) type 3 ordinary chondrites. Colony and ALHA 77307 have atypical TL properties, including very low TL sensitivity, suggesting that phosphors other than feldspar are important. They have apparently experienced less metamorphism than the others, and may have also been aqueously altered.     

Thermoluminescence and the shock and reheating history of meteorites—II: Annealing studies of the Kernouve meteorite

Samples of the unshocked, equilibrated chondrite, Kernouve (H6), have been annealed for 1–100 hours at 500–1200°C, their thermoluminescence sensitivity measured and Na, K, Mn, Ca and Sc determined by instrumental neutron activation analysis. The TL sensitivity decreased with temperature until by 1000°C it had fallen by 40%. The process responsible has an activation energy of ~8 kcal/mole and probably involves diffusion. Samples annealed 1000–1200°C had TL sensitivities 10^?2 times the unannealed values, most of the decrease occurring ~1100°C. This process has an activation energy of ~100 kcal/mole and is probably related to the melting of the TL phosphor, feldspar, with some decomposition and loss of Cs, Na and K. Meteorites whose petrography indicates healing > 1100°C by natural shock heating events (shock facies d-f). have TL sensitivities similar to samples annealed > 1100°C. Our own and literature compositional data indicate that TL is more stable to annealing than Ag, In, Tl, Bi, Zn and Te and less stable than Na, K, Mn, Ca, Se and Co, while the TL decrease resembles very closely the pattern of Cs loss on annealing.     

Thermoluminescence spectra of igneous quartz and hydrothermal vein quartz

Variations in thermoluminescence spectra are reported for four types of geological quartz examined with a new spectrometer featuring dual imaging photon detectors that separately and simultaneously detect (1) uv-blue (200–450 nm) and (2) blue to near infrared (400–800 nm) emission. Samples show striking differences which appear to be characteristic of their geological origin. Volcanic quartz phenocrysts from acid volcanics show red thermoluminescence (TL) emission bands centered at 620–630 nm that are 100 times more intense than similar bands in other quartz, while a violet emission at 420–435 nm was observed exclusively in igneous quartz (volcanic and granitic). A broad emission band centered at 560–580 nm was observed only in quartz formed hydrothermally. Massive quartz from Li-rich pegmatite bodies shows narrow, intense 470 nm emission bands at 230° C apparently related to Al and to Ge defects detected with electron paramagnetic resonance (EPR), and emission bands at 330 and 280 nm, possibly related to recombination at oxygen vacancies. The common 380 nm emission band of quartz was observed in both volcanic and granitic quartz, but was not detected in either the pegmatitic or the hydrothermal vein quartz. Observed spectral variation is identified as a potential source of error in luminescence dating.     

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     

Tracing hydrothermal mineral thenardite in geysers/hot springs of North-western Himalayan belt,Ladakh Geothermal Province,India by hydrogeochemistry,fluid-mineral equilibria and isotopic studies

The present study highlights the first evidence of hydrothermal mineral Thenardite (Na₂SO₄) from Puga geothermal area, North-western Himalayan belt in Ladakh Geothermal Province, India, which is unequivocal evidence for the presence of high-temperature hydrothermal fluid activity from one of the thickest crust areas of the Earth. The Puga geothermal belt illustrates a fault-bounded hydrothermal system with a clearly defined conductive zone, coinciding with Kiagar Tso fault typically exemplifying a shallow-level medium enthalpic geothermal reservoir. The hydrogeochemistry suggests that thermal and non-thermal waters are of Na-Cl-HCO₃ and Ca-Mg-HCO₃ type, respectively, with neutral to near alkaline pH. The silica and cation geothermometry reveal sub-surface temperatures around 150 °C and 250 °C, respectively, at shallow depth; however, >250 °C is anticipated at the deepest levels (~3 km). Stable isotope (δD and δ¹⁸O) studies explicate depletion of isotopic content for thermal waters over Puga river water and radiogenic isotope (³H) suggests matured thermal waters with ongoing water-rock interactions. The recharge altitude estimation and physiographic studies put forth that geothermal reservoir is recharged with the ice masses located at an altitude of 6458 m above mean sea level (msl) in the west of Puga valley, probably from the highest peak of Polokong La mountain. The two key processes participating in regulation of proportions of the dissolved salts in the thermal waters are silicate weathering and ion-exchange kinetics. The powder X-ray diffraction study reveals a major occurrence of hydrothermal mineral thenardite in the hot spring deposits for the first time along with huge encrustations of trona, borax, calcite and elemental sulfur. The high-temperature fluids encounter thenardite, pyrite, and jarosite-bearing minerals in basement rock causing enrichment of SO₄²⁻ and Cl⁻ in geothermal waters. The temperature-dependent speciation modelling (50 °C–200 °C) for major ion Na⁺ reveals the composition of the reservoir fluid (~150 °C): Na⁺ > NaCO₃⁻ > NaSO₄⁻ > NaHCO₃ > NaF > NaOH. A conceptual evolution model of thermal waters involving the recharge-deep circulation-mixing-discharge of thermal springs is hence put forth in the study using various hydrogeochemical insights.     

Structural changes and oxidation of ferroan phlogopite with increasing temperature: in situ neutron powder diffraction and Fourier transform infrared spectroscopy

The thermal response of the natural ferroan phlogopite-1M, K₂(Mg_4.46Fe_0.83Al_{0. 34}Ti_0.22)(Si_5.51Al_{2. 49})O₂₀[OH_3.59F_0.41] from Quebec, Canada, was studied with an in situ neutron powder diffraction. The in situ temperature conditions were set up at ?263, 25, 100°C and thereafter at a 100°C intervals up to 900°C. The crystal structure was refined by the Rietveld method (R _p=2.35–2.78%, R _wp=3.01–3.52%). The orientation of the O–H vector of the sample was determined by the refinement of the diffraction pattern. With increasing temperature, the angle of the OH bond to the (001) plane decreased from 87.3 to 72.5°. At room temperature, a = 5.13 Å, b = 9.20 Å, c = 10.21 Å, β = 100.06° and V(volume) = 491.69 ų. The expansion rate of the unit cell dimensions varied discontinuously with a break at 500°C. The shape of the M-octahedron underwent some significant changes such as flattening at 500°C. At temperatures above 500°C, the octahedral thickness and mean distance was decreased, while the octahedral flattening angle increased. Those results were attributed to the Fe oxidation and dehydroxylation processes. The dehydroxylation mechanism of the ferroan phlogopite was studied by the Fourier transform infrared spectroscopy (FTIR) after heated at temperatures ranging from 25 to 800°C with an electric furnace in a vacuum. In the OH stretching region, the intensity of the OH band associated with Fe²⁺(N _B-band) begun to decrease outstandingly at 500°C. The changes of the IR spectra confirmed that dehydroxylation was closely related to the oxidation in the vacuum of the ferrous iron in the M-octahedron. The decrease in the angle of the OH bond to the (001) plane, with increasing temperature, might be related to the imbalance of charge in the M-octahedra due to Fe oxidation.     

Conditions for the origin of oxidized carbonate-silicate melts: Implications for mantle metasomatism and diamond formation

An experimental study on the origin of ferric and ferrous carbonate-silicate melts, which can be considered as the potential metasomatic oxidizing agents and diamond forming media, was performed in the (Ca,Mg)CO₃-SiO₂-Al₂O₃-(Mg,Fe)(Cr,Fe,Ti)O₃ system, at 6.3 GPa and 1350–1650 °C. At 1350–1450 °C and ?O₂ of FMQ + 2 log units, carbonate–silicate melt, coexisting with Fe^3 +-bearing ilmenite, pyrope-almandine and rutile, contained up to 13 wt.% of Fe₂O₃. An increase in the degree of partial melting was accompanied by decarbonation and melt enrichment with CO₂, up to 21 wt.%. At 1550–1650 °C excess CO₂ segregated as a separate fluid phase. The restricted solubility of CO₂ in the melt indicated that investigated system did not achieve the second critical point at 6.3 GPa. At 1350–1450 °C and ?O₂ close to CCO buffer, Fe^2 +-bearing carbonate–silicate melt was formed in association with pyrope-almandine and Fe^3 +-bearing rutile. It was experimentally shown that CO₂-rich ferrous carbonate-silicate melt can be an effective waterless medium for the diamond crystallization. It provides relatively high diamond growth rates (3–5 μm/h) at P,T-conditions, corresponding to the formation of most natural diamonds.     

Time–temperature evolution of microtextures and contained fluids in a plutonic alkali feldspar during heating

Microtextural changes brought about by heating alkali feldspar crystals from the Shap granite, northern England, at atmospheric pressure, have been studied using transmission and scanning electron microscopy. A typical unheated phenocryst from Shap is composed of about 70 vol% of tweed orthoclase with strain-controlled coherent or semicoherent micro- and crypto-perthitic albite lamellae, with maximum lamellar thicknesses <1 μm. Semicoherent lamellae are encircled by nanotunnel loops in two orientations and cut by pull-apart cracks. The average bulk composition of this microtexture is Ab_27.6Or_71.8An_0.6. The remaining 30 vol% is deuterically coarsened, microporous patch and vein perthite composed of incoherent subgrains of oligoclase, albite and irregular microcline. The largest subgrains are ~3 μm in diameter. Heating times in the laboratory were 12 to 6,792 h and T from 300°C into the melting interval at 1,100°C. Most samples were annealed at constant T but two were heated to simulate an ⁴⁰Ar/³⁹Ar step-heating schedule. Homogenisation of strain-controlled lamellae by Na↔K inter-diffusion was rapid, so that in all run products at >700°C, and after >48 h at 700°C, all such regions were essentially compositionally homogeneous, as indicated by X-ray analyses at fine scale in the transmission electron microscope. Changes in lamellar thickness with time at different T point to an activation energy of ~350 kJmol⁻¹. A lamella which homogenised after 6,800 h at 600°C, therefore, would have required only 0.6 s to do so in the melting interval at 1,100°C. Subgrains in patch perthite homogenised more slowly than coherent lamellae and chemical gradients in patches persisted for >5,000 h at 700°C. Homogenisation T is in agreement with experimentally determined solvi for coherent ordered intergrowths, when a 50–100°C increase in T for An₁ is applied. Homogenisation of lamellae appears to proceed in an unexpected manner: two smooth interfaces, microstructurally sharp, advance from the original interfaces toward the mid-line of each twinned, semicoherent lamella. In places, the homogenisation interfaces have shapes reflecting the local arrangements of nanotunnels or pull-aparts. Analyses confirm that the change in alkali composition is also relatively sharp at these interfaces. Si–Al disordering is far slower than alkali homogenisation so that tweed texture in orthoclase, tartan twinning in irregular microcline, and Albite twins in albite lamellae and patches persisted in all our experiments, including 5,478 h at 700°C, 148 h at 1,000°C and 5 h at 1,100°C, even though the ensemble in each case was chemically homogeneous. Nanotunnels and pull-aparts were modified after only 50 min at 500°C following the simulated ⁴⁰Ar/³⁹Ar step-heating schedule. New features called ‘slots’ developed away from albite lamellae, often with planar traces linking slots to the closest lamella. Slot arrays were often aligned along ghost-like regions of diffraction contrast which may mark the original edges of lamellae. We suggest that the slot arrays result from healing of pull-aparts containing fluid. At 700°C and above, the dominant defects were subspherical ‘bubbles’, which evolved from slots or from regions of deuteric coarsening. The small degree of partial melting observed after 5 h at 1,100°C was often in the vicinity of bubbles. Larger micropores, which formed at subgrain boundaries in patch perthite during deuteric coarsening, retain their shape up to the melting point, as do the subgrain boundaries themselves. It is clear that modification of defects providing potential fast pathways for diffusion in granitic alkali feldspars begins below 500°C and that defect character progressively changes up to, and beyond, the onset of melting.     

New constraints on granulite facies metamorphism and melt production in the Lewisian Complex,northwest Scotland

In this study, we investigate the metamorphic history of the Assynt and Gruinard blocks of the Archean Lewisian Complex, northwest Scotland, which are considered by some to represent discrete crustal terranes. For samples of mafic and intermediate rocks, phase diagrams were constructed in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) system using whole‐rock compositions. Our results indicate that all samples equilibrated at similar peak metamorphic conditions of ~8–10 kbar and ~900–1,000°C, consistent with field evidence for in situ partial melting and the classic interpretation of the central region of the Lewisian Complex as representing a single crustal block. Melt‐reintegration modelling was employed in order to estimate probable protolith compositions. Phase equilibria calculated for these modelled undepleted precursors match well with those determined for a subsolidus amphibolite from Gairloch in the southern region of the Lewisian Complex. Both subsolidus lithologies exhibit similar phase relations and potential melt fertility, with both expected to produce orthopyroxene‐bearing hornblende granulites, with or without garnet, at the conditions inferred for the Badcallian metamorphic peak. For fully hydrated protoliths, prograde melting is predicted to first occur at ~620°C and ~9.5 kbar, with up to 45% partial melt predicted to form at peak conditions in a closed‐system environment. Partial melts calculated for both compositions between 610 and 1,050°C are mostly trondhjemitic. Although the melt‐reintegrated granulite is predicted to produce more potassic (granitic) melts at ~700–900°C, the modelled melts are consistent with the measured compositions of felsic sheets from the central region Lewisian Complex.     

P–T evolution and episodic zircon growth in barroisite eclogites of the Lanterman Range,northern Victoria Land,Antarctica

Prograde P–T–t paths of eclogites are often ambiguous owing to high variance of mineral assemblages, large uncertainty in isotopic age determinations and/or variable degree of retrograde equilibration. We investigated these issues using the barroisite eclogites from the Lanterman Range, northern Victoria Land, Antarctica, which are relatively uncommon but free of retrogression. These eclogites revealed three stages of prograde metamorphism, defining two distinctive P–T trajectories, M_1–2 and M₃. Inclusion minerals in garnet porphyroblasts suggest that initial prograde assemblages (M₁) consist of garnet+omphacite+barroisite/Mg‐pargasite+epidote+phengite+paragonite+rutile/titanite+quartz, and subsequent M₂ assemblages of garnet+omphacite+barroisite+phengite+rutile±quartz. The inclusion‐rich inner part of garnet porphyroblasts preserves a bell‐shaped Mn profile of the M₁, whereas the inclusion‐poor outer part (M₂) is typified by the outward decrease in Ca/Mg and X_Fe (=Fe²⁺/(Fe²⁺+Mg)) values. A pseudosection modelling employing fractionated bulk‐rock composition suggests that the eclogites have initially evolved from ~15 to 20 kbar and 520–570°C (M₁) to ~22–25 kbar and 630–650°C (M₂). The latter is in accordance with P–T conditions estimated from two independent geothermobarometers: the garnet–clinopyroxene–phengite (~25 ± 3 kbar and 660 ± 100°C) and Zr‐in‐rutile (~650–700°C at 22–27 kbar). The second segment (M_3A–B) of prograde P–T path is recorded in the grossular‐rich overgrowth rim of garnet. Apart from disequilibrium growth of the M_3A garnet, ubiquitous overgrowth of the M_3B garnet permits us to estimate the P–T conditions at ~26 ± 3 kbar and 720 ± 80°C. The cathodoluminescence (CL) imaging of zircon grains separated from a barroisite eclogite revealed three distinct zones with bright rim, dark mantle and moderately dark core. Eclogitic phases such as garnet, omphacite, epidote and rutile are present as fine‐grained inclusions in the mantle and rim of zircon, in contrast to their absence in the core. The sensitive high‐resolution ion microprobe U–Pb dating on metamorphic mantle domains and neoblasts yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 515 ± 4 Ma (tσ), representing the time of the M₂ stage. On the other hand, overgrowth rims as well as bright‐CL neoblasts of zircon were dated at 498 ± 11 Ma (tσ), corresponding to the M₃. Average burial rates estimated from the M₂ and M₃ ages are too low (<2 mm/year) for cold subduction regime (~5–10°C/km), suggesting that an exhumation stage intervened between two prograde segments of P–T path. Thus, the P–T–t evolution of barroisite eclogites is typified by two discrete episodes with an c. 15 Ma gap during the middle Cambrian subduction of the Antarctic Ross Orogeny.     

Recovery of Zn from wastewater of zinc plating industry by precipitation of doped ZnO nanoparticles

In this study, a facile precipitation process to treat wastewater from zinc plating industry is presented. Water purification rates of Zn range between 96.40 % and 99.99 % depending on the reaction conditions. Optimal results are gained at a low pH value of 9, low temperature of 40 °C and a fast alkalization using NaOH solution containing 16 % pure NaOH. Traces of Ni, Fe, Zn, Cu and Cr present in the wastewater were almost completely removed. The precipitates were analysed by X-ray diffraction, infrared and Raman spectroscopy, electron microscopy and magnetic measurements. They consist of doped ZnO as a main phase. Although ZnO exclusively crystallizes in nanoparticle size, the morphology is directly influenced by the experimental parameters. Additionally, very small amounts of ZnCO₃ and Zn(OH)₂ were detected. Magnetic investigations indicate the incorporation of Ni and Fe into the ZnO lattice. The measured saturation magnetization is ~0.01 emu/g and the Curie temperature is ~75 °C.     

Thermal decomposition of Ferrian chamosite: an infrared emission spectroscopic study

The thermal behaviour of ripidolite, an iron-rich chlorite, has been studied in situ by infrared emission spectroscopy up to 800 °C. The more di,trioctahedral nature due to significant amounts of Fe³⁺ is reflected, in addition to the two bands around 3420 and 3560 cm⁻¹, by an extra band around 3345 cm⁻¹. This extra band is absent in pure dioctahedral chlorites without Fe³⁺. These bands have been assigned to (AlAl)O-OH, (SiAl)O-OH and (SiSi)O-OH stretching modes with increasing frequencies. The bands disappear upon dehydroxylation around 650 °C. A similar behaviour is observed for the corresponding libration modes around 716, 759 and 802 cm⁻¹. The stretching and bending modes of the inner-OH of the octahedral sheet in the 2:1 clay-like layer are observed around 3645, 943 and 904 cm⁻¹. Although the bands decrease in intensity, they remain present up to 800 °C as dehydroxylation of the octahedral sheet is not yet complete at this temperature. The presence of two bending modes is explained as being due to a differentiation between Mg-OH and Fe-OH modes. At 650 °C a new sharp band is observed around 502 cm⁻¹ assigned to a (Fe,Mg)-O-Al bending mode caused by the formation of a spinel-like interlayer phase after dehydroxylation. Received: 4 June 1999 / Accepted: 6 August 1999     

Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure

We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm^?1 display a small frequency lowering (<4 cm^?1) and a moderate broadening (<10 cm^?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm^?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm^?1 respectively) and broadening (~30 cm^?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm^?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm^?1, at ?194 °C. They exhibit significant frequency increase (~20 cm^?1) and broadening (~70 cm^?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)_Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm^?1 (type (2); 3,550 cm^?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)_Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.     

Thermoluminescence and the shock and reheating history of meteorites—III: The shergottites

The thermoluminescence (TL) sensitivities of the four shergottites are extremely low and display a 10-fold range (values are 0.15 to 1.8, where Dhajala = 1000), with the TL sensitivity decreasing with increasing peak temperature (from about 140 to 180°C) and peak width (from about 100 to 150°C). A mineral separation experiment indicates that the mineral producing the TL is associated with the maskelynite, presumably nanogram per gram quantities of crystalline feldspar are present in the maskelynite. Samples of Shergotty, Allan Hills A77005 and Elephant Moraine A79001 were annealed at 400–900°C for 24–98 h. For Shergotty, the peak increased in width and moved to higher temperatures in the glow-curve, while for Allan Hills A77005 and Elephant Moraine A79001, whose TL peaks were already broad and at high temperatures, remained unchanged. All samples showed a significant increase in TL sensitivity when annealed at >600–700°C. Apparently, the feldspar is present in varying proportions of high to low-temperature form and in amounts which vary from meteorite to meteorite. We conclude that the shergottites underwent post-shock recrystallization at a variety of cooling rates and that the order of increasing cooling rate was Shergotty, Allan Hills A77005, Zagami and Elephant Moraine A79001. The presence of a high-temperature phase implies peak post-shock cooling temperatures >600°C and that the size of the ejecta was <10 m. Current theories are well able to explain the ejection of such small objects from Mars.     

Structural thermal behavior of paragonite and its dehydroxylate: a high-temperature single-crystal study

 The lattice constants of paragonite-2M₁, NaAl₂(AlSi₃)O₁₀(OH)₂, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: α_a = 1.51(8) × 10⁻⁵, α_b = 1.94(6) × 10⁻⁵, α_c = 2.15(7) ×  10⁻⁵ °C⁻¹, and α_V = 5.9(2) × 10⁻⁵ °C⁻¹. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl₂ (AlSi₃)O₁₁, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V ₀ = 1 + 5.9(2) × 10⁻⁵ T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999     

The investigation of defects in shock-metamorphosed quartz

The shock-metamorphosed quartz exhibits thermal luminescence (TL) with maxima at 365 nm, 470 nm and 610–680 nm. By electron paramagnetic resonance (EPR) analysis E₁ type electron centers and hole centers have been found which originate from vacancies including those from the substitution of Al³⁺ and/or Fe³⁺, for Si⁴⁺. The EPR and TL spectra may be interpreted mainly in terms of vacancy type defects associated with dislocations in the crystal structure of quartz.