Recrystallisation rims in zircon (Valle d'Arbedo, Switzerland): an integrated cathodoluminescence, LA-ICP-MS, SHRIMP, and TEM study

Recrystallization rims are a common feature of zircon crystals that underwent metamorphism. We present a microstructural and microchemical study of partially recrystallized zircon grains collected in polymetamorphic migmatites (Valle d'Arbedo, Ticino, Switzerland). The rims are bright in cathodo-luminescence (CL), with sharp and convex contacts characterized by inward-penetrating embayments transgressing igneous zircon cores. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data and transmission electron microscopy (TEM) imaging indicate that the rims are chemically and microstructurally different from the cores. The rims are strongly depleted in REE, with concentrations up to two orders of magnitude lower than in the cores, indicating a significant loss of REE during zircon recrystallization. Enrichment in non-formula elements, such as Ca, has not been observed in the rims. The microstructure of zircon cores shows a dappled intensity at and below the 100 nm scale, possibly due to radiation damage. Other defects such as pores and dislocations are absent in the core except at healed cracks. Zircon rims are mostly dapple-free, but contain nanoscale pores and strain centers, interpreted as fluid inclusions and chemical residues, respectively. Sensitive high-resolution ion microprobe (SHRIMP) U-Pb ages show that the recrystallization of the rims took place >200 Ma ago when the parent igneous zircon was not metamict. The chemical composition and the low-Ti content of the rims indicate that they form at sub-solidus temperatures (550-650 degrees C). Recrystallization rims in Valle d'Arbedo zircon are interpreted as the result of the migration of chemical reaction fronts in which fluid triggered in situ and contemporaneous interface-coupled dissolution-reprecipitation mechanisms. This study indicates that strong lattice strain resulting from the incorporation of a large amount of impurities and structural defects is not a necessary condition for zircon to recrystallize. Our observations suggest that the early formation of recrystallization rims played a major role in preserving zircon from the more recent Alpine metamorphic overprint.

1st radiometric dating of a paleontologically dated Bathonian level from Georgia (USSR) - Use of the cathodoluminescence for selection of suitable plagioclases

Jurassic volcanic formations interlayered with (ammonite-bearing) sediments are common in the Caucasus area; this situation is of interest for the numerical calibration of the poorly documented Jurassic portion of the time scale. However, following petrographic study on thin sections no whole-rocks can be considered reliable geochronometers due to subsequent alteration; from about 20 samples, two were selected for plagioclase dating; one (V134) is probably early Kimmeridgian in age; the other (V136) is probably located in the Lower Bathonian stage according to diagnostic ammonites. Cathodoluminescence (CTL) study has shown that sample V136 was similar to usual volcanic feldspars (blue to green colour); however, the lack of CTL of the V134 plagioclase is a character common to diagenetic feldspars; consequently, in spite of a good optical preservation, this geo-chronometer cannot give an age representative of the time of emplacement of the lava flow. We have combined CTL observation with microprobe analysis in order to document the poorly known CTL behaviour of volcanic feldspars; cations Ti4+ and Fe2+ play a major role in the CTL colour of plagioclases and are able to document the growing history of these feldspars ; phenocrysts are initially rich in Fe2+ (core of the crystals, green in colour), then richer in Ti toward the exterior; microcrysts are even richer in Ti (blue to bright blue). We have also observed that natural CTL colour was modified resulting from acid ``cleaning'' of the separated feldspars : the initial blue or green colour tends to change to yellow or violet, respectively, after acid treatment probably due to oxydation of Fe2+ toward Fe3+. X-ray and microprobe analyses both indicated that plagioclases from sample V134 was near the sodic end member (albite) suggesting a diagenetic origin in this andesitic basalt; In contrast, sample V136 contains a calcic plagioclase of common composition for a doleritic basalt. The K-Ar conventional technique was applied as a preliminary tool for radiometric analysis. The Kimmeridgian Na-plagioclase sample gave a ``rejuvenated'' (85 Ma) apparent age which confirms a late genesis for the separated plagioclase phase; this interpretation is based on CTL observation, X-ray analysis, and microprobe analysis ; these techniques are able to distinguish samples which have been submitted to diagenetic alteration from those which have not. An age consistent with the stratigraphic location has been obtained from sample V136. This age of 161 +/- 3 (2-sigma) Ma, is the first one available from a sample palaeontologically located with reasonable precision within the mid Jurassic time.

Defect study of SnO2 nanostructures by cathodoluminescence analysis: Application to nanowires

Defects in SnO2 nanowires have been studied by cathodoluminescence, and the obtained spectra have been compared with those measured on SnO2 nanocrystals of different sizes in order to reveal information about point defects not determined by other characterization techniques. Dependence of the luminescence bands on the thermal treatment temperatures and pre-treatment conditions have been determined pointing out their possible relation, due to the used treatment conditions, with the oxygen vacancy concentration. To explain these cathodoluminescence spectra and their behavior, a model based on first-principles calculations of the surface oxygen vacancies in the different crystallographic directions is proposed for corroborating the existence of surface state bands localized at energy values compatible with the found cathodoluminescence bands and with the gas sensing mechanisms. CL bands centered at 1.90 and 2.20 eV are attributed to the surface oxygen vacancies 100° coordinated with tin atoms, whereas CL bands centered at 2.37 and 2.75 eV are related to the surface oxygen vacancies 130° coordinated. This combined process of cathodoluminescence and ab initio calculations is shown to be a powerful tool for nanowire defect analysis.

Quantum mechanical modeling of excited electronic states and their relationship to cathodoluminescence of BaZrO3

First-principles calculations set the comprehension over performance of novel cathodoluminescence (CL) properties of BaZrO3 prepared through microwave-assisted hydrothermal. Ground (singlet, s*) and excited (singlet s** and triplet t**) electronic states were built from zirconium displacement of 0.2 Å in {001} direction. Each ground and excited states were characterized by the correlation of their corresponding geometry with electronic structures and Raman vibrational frequencies which were also identified experimentally. A kind of optical polarization switching was identified by the redistribution of 4dz2 and 4dxz (Zr) orbitals and 2pz O orbital. As a consequence, asymmetric bending and stretching modes theoretically obtained reveal a direct dependence with their polyhedral intracluster and/or extracluster ZrO6 distortions with electronic structure. Then, CL of the as-synthesized BaZrO3 can be interpreted as a result of stable triplet excited states, which are able to trap electrons, delaying the emission process due to spin multiplicity changes. © 2013 AIP Publishing LLC.

Morphological ripening of fluid inclusions and coupled zone-refining in quartz crystals revealed by cathodoluminescence imaging: Implications for CL-petrography, fluid inclusion analysis and trace-element geothermometry

Cathodoluminescence (CL) studies have previously shown that some secondary fluid inclusions in luminescent quartz are surrounded by dark, non-luminescent patches, resulting from fracture-sealing by late, trace-element-poor quartz. This finding has led to the tacit generalization that all dark CL patches indicate influx of low temperature, late-stage fluids. In this study we have examined natural and synthetic hydrothermal quartz crystals using CL imaging supplemented by in-situ elemental analysis. The results lead us to propose that all natural, liquid-water-bearing inclusions in quartz, whether trapped on former crystal growth surfaces (i.e., of primary origin) or in healed fractures (i.e., of pseudosecondary or secondary origin), are surrounded by three-dimensional, non-luminescent patches. Cross-cutting relations show that the patches form after entrapment of the fluid inclusions and therefore they are not diagnostic of the timing of fluid entrapment. Instead, the dark patches reveal the mechanism by which fluid inclusions spontaneously approach morphological equilibrium and purify their host quartz over geological time. Fluid inclusions that contain solvent water perpetually dissolve and reprecipitate their walls, gradually adopting low-energy euhedral and equant shapes. Defects in the host quartz constitute solubility gradients that drive physical migration of the inclusions over distances of tens of μm (commonly) up to several mm (rarely). Inclusions thus sequester from their walls any trace elements (e.g., Li, Al, Na, Ti) present in excess of equilibrium concentrations, thereby chemically purifying their host crystals in a process analogous to industrial zone refining. Non-luminescent patches of quartz are left in their wake. Fluid inclusions that contain no liquid water as solvent (e.g., inclusions of low-density H2O vapor or other non-aqueous volatiles) do not undergo this process and therefore do not migrate, do not modify their shapes with time, and are not associated with dark-CL zone-refined patches. This new understanding has implications for the interpretation of solids within fluid inclusions (e.g., Ti- and Al-minerals) and for the elemental analysis of hydrothermal and metamorphic quartz and its fluid inclusions by microbeam methods such as LA-ICPMS and SIMS. As Ti is a common trace element in quartz, its sequestration by fluid inclusions and its depletion in zone-refined patches impacts on applications of the Ti-in-quartz geothermometer.

On the overabundance of light rare earth elements in terrestrial zircons and its implication for Earth's earliest magmatic differentiation

We present whole-rock and zircon rare earth element (REE) data from two early Archaean gneisses (3.81 Ga and 3.64 Ga) from the Itsaq gneiss complex, south-west Greenland. Both gneisses represent extremely rare examples of unaltered, fresh and relatively undeformed igneous rocks of such antiquity. Cathodoluminescence imaging of their zircons indicates a single crystallisation episode with no evidence for either later metamorphic and/or anatectic reworking or inheritance of earlier grains. Uniform, single-population U/Pb age data confirm the structural simplicity of these zircons. One sample, a 3.64 Ga granodioritic gneiss from the Gothabsfjord, yields a chondrite-normalised REE pattern with a positive slope from La to Lu as well as substantial positive Ce and slight negative Eu anomalies, features generally considered to be typical of igneous zircon. In contrast, the second sample, a 3.81 Ga tonalite from south of the Isua Greenstone Belt, has variable but generally much higher light REE abundances, with similar middle to heavy REE. Calculation of zircon/melt distribution coefficients (D-REE(zircon/melt)) from each sample yields markedly different values for the trivalent REE (i.e. Ce and Eu omitted) and simple application of one set of D-REE(zircon/melt) to model the melt composition for the other sample yields concentrations that are in error by up to two orders of magnitude for the light REE (La-Nd). The observed light REE overabundance in the 3.81 Ga tonalite is a commonly observed feature in terrestrial zircons for which a number of explanations ranging from lattice strain to disequilibrium crystallisation have been proposed and are further investigated herein. Regardless of the cause of light REE overabundance, our study shows that simple application of zircon/melt distribution coefficients is not an unambiguous method for ascertaining original melt composition. In this context, recent studies that use REE data to claim that > 4.3 Ga Hadean detrital zircons originally crystallised from an evolved magma, in turn suggesting the operation of geological processes in the early Earth analogous to those of the present day (e.g. subduction and melting of hydrated oceanic crust), must be regarded with caution. Indeed, comparison of terrestrial Hadean and > 3.9 Ga lunar highland zircons shows remarkable similarities in the light REE, even though subduction processes that have been used to explain the terrestrial zircons have never operated on the Moon. (C) 2002 Elsevier Science B.V. All rights reserved.

MOVPE growth and characterisation of ZnO properties for optoelectronic applications

ZnO, Epitaxy, Metal organic vapor phase epitaxy, MOCVD, CVD, Semiconductor, Optoelectronics, X-ray diffraction, Cathodoluminescence, Microelectronics

Oxygen isotope thermometry in carbonatites, Fuerteventura, Canary Islands, Spain

Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960degreesC (average 710degreesC). The highest temperature is obtained from pyroxene-calcite pairs. The above range is in agreement with other carbonatite thermometric Studies. This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite-carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar-Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite-carbonatite magmas.

Evidence of growth and sector zoning in hydrothermal quartz from Alpine veins

Several quartz crystals from three different Alpine vein localities and of known petrologic setting and evolution have been examined for possible elemental sector zoning in order to help to constrain the mechanisms of such trace element incorporation. Using different in situ techniques (EMPA, LA-ICPMS, SIMS, FTIR-spectroscopy), it was established that Al and Li concentrations can exceed several hundreds of ppma for distinct growth zones within crystals formed at temperatures of about 300 degrees C or less and that also display patterns of cyclic growth when examined with cathodoluminescence. In contrast, crystals formed at temperatures closer to 400 degrees C and without visible cyclic growth have low concentrations of Al and Li as well as other trace elements. Al and Li contents are correlated along profiles measured within the crystals and in general their proportion does not change along the profiles. No relationships were found between Al, Na, and K, and germanium has a qualitative relationship with Al. FTIR spectra also show OH(-) absorption bands within the quartz, with higher amplitudes in zones rich in Al and Li. Sector zoning is present. It is most pronounced between prismatic and rhombohedral faces of the same growth zone, but also between the rhombohedral faces of r and z, which contain different amounts of trace elements. The sector zoning is also expressed by changes in the Li/Al ratio, with higher ratios in 17 compared to r faces. It is concluded that the incorporation of trace elements into hydrothermal quartz from Alpine veins is influenced by growth mechanisms and surface-structures of the growing quartz crystals, the influence of which may change as a function of temperature, pH, as well as the chemical composition of the fluid.

The origin of black colouration in onyx agate from Mali

Natural onyx agate from Mali was investigated in an integrated mineralogical and chemical study to reveal the origin of the unusual black colouration. Detailed studies by polarizing microscopy, scanning electron microscopy and micro-Raman spectroscopy showed that the colour of the dark bands is related to the incorporation of small particles of carbon (low-crystalline graphite) up to 200 nm in size into the cryptocrystalline silica matrix. The dark bands have carbon contents of 1.88 wt.%. The location of the graphite particles is closely related to the primary structural banding in the chalcedony. Cathodoluminescence data shows that the banding is interrupted by small fissures containing secondary hydrothermal quartz. The carbon isotope composition (delta C-13 value of -31.1+/-0.2 parts per thousand) of the carbonaceous material points to an organic precursor. Both the direct hydrothermal formation of graphite from methane under elevated temperature and the graphitization of organic precursors by secondary hydrothermal or metamorphic overprint are possible explanations for the colour of the dark bands. The graphitization of organic precursors results in an intense electron spin resonance line at g(eff) = 2.0026.