Blue Cathodoluminescence Research Articles

Mineralization Characteristics of the Hokuryu Epithermal Au‐Ag Deposit, Hokkaido, Japan

ABSTRACTVeins intersected by a ~600‐m‐long drill core into the Hokuryu epithermal Au‐Ag deposit in the northeastern part of Hokkaido, Japan, were investigated including mineralogy, texture, quartz composition, and fluid inclusion characteristics, with relation to elevation. Host rocks of these veins are flow‐banded rhyolite, pyroclastic breccia, and andesite and are mainly altered by illite and chlorite. The veins display crustiform and massive macroscopic textures. The crustiform veins generally located at higher elevations, contain Ag‐rich and Au‐Ag‐rich bands. The massive veins are mainly present at lower elevations, and they are generally barren of precious metals. The Ag‐rich bands in the crustiform veins contain mineral assemblage of hessite + sphalerite + pyrite + galena. These minerals, together with anhedral to rhombic adularia, exist within the interstices of quartz that display microspherical texture. The Au‐Ag‐rich bands contain mineral assemblage of electrum ± naumannite‐aguilarite associated with quartz with colloform, ghost‐sphere, and ghost‐bladed textures. Bulk compositions of the veins reflect the ore mineralogy observed in which Ag is strongly correlated with Pb, Te, Zn, Cd, and Bi. The barren massive veins are mainly composed of granular quartz. Textural and mineralogical characteristics of Au‐ and Ag‐bearing bands in the crustiform veins indicate amorphous silica and calcite precursors. Together with the coexistence of adularia, these suggest liquid boiling during vein formation. Quartz associated with Au‐ and Ag‐bearing minerals exhibits blue cathodoluminescence (ca. 400 nm wavelength) triggered by high Al impurity probably due to pH and pressure fluctuations or impurity redistribution during recrystallization from metastable amorphous silica. Fluid inclusions hosted in quartz and adularia, which contain negligible amounts of CO2, show a modal homogenization temperature range of 260°C–290°C and a salinity range of 1.2–6.9 wt% NaCl equivalent. The homogenization temperatures follow a boiling point curve and indicate an erosion of up to ~340 m for the deposit. The variable salinities in relation to elevation suggest extreme vapor loss during boiling at depth, episodic influx of high salinity fluids from deeper source, or mixing with high salinity fluids along anastomosing fractures at relatively shallower depths.

The 450 nm (2.8 eV) cathodoluminescence emission in quartz and its relation to structural defects and Ti contents

Abstract The origin of the common blue 450 nm (2.8 eV) cathodoluminescence (CL) emission in natural and synthetic quartz has been investigated using a combination of CL microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and trace-element analysis by electron micro-probe analysis as well as inductively coupled plasma-mass spectrometry (ICP-MS). The study shows that the appearance of the ~450 nm emission band can be attributed to two different defects in quartz. First, a transient luminescence can be explained by structural defects in oxygen deficient quartz. The luminescence model implies self-trapped exciton (STE) emission related to oxygen vacancies. This type of CL emission is frequent in high-purity synthetic quartz and natural quartz of hydrothermal origin. Second, in Ti-rich quartz from natural samples (e.g., quartz phenocrysts in rhyolites) and synthetic quartz of Ti-diffusion experiments, an additional 450 nm (2.8 eV) emission was detected, which is stable under the electron beam. The intensity of this ~450 nm emission band correlates with the concentration of trace Ti in quartz, and substitutional Ti4+ at the Si4+ position was proved by EPR spectroscopy. In quartz crystals with elevated Ti concentrations both intrinsic and extrinsic blue CL emissions at ~450 nm can coexist, hindering a thorough characterization and quantification of the CL signal. A reliable distinction of the two different CL emission bands is possible by fitting the peaks of the CL spectra, and the peak width of the 450 nm emission can be used to differentiate the STE from the Ti4+ emission. However, the definitive technique is through the observation of CL peak shape change over time at a point by collecting a time series of CL spectra in conjunction with EPR spectroscopy and trace-element analysis of the Ti concentration.

Polymetallic tungsten skarn mineralisation related to the Periadriatic intrusion at Lienzer Schlossberg, East Tyrol, Austria

Abstract A regional tungsten anomaly was discovered and explored in the Lienzer Schlossberg area that is part of the crystalline Austroalpine nappe complex of the Eastern Alps in the 1970/80-ties. Tungsten is present as scheelite, which occurs in steeply SSW dipping WNW-ENE oriented quartz veinlets and joints within the porphyritic dioritic to tonalitic/granodioritic host rocks of the Oligocene Lienz/Edenwald intrusion and in the exoskarn, which developed at the contact of the intrusion with Ca-rich lithologies. The skarn system is characterised by two stages: (1) a primary high-temperature calc-silicate stage characterised by grossular, diopside-hedenbergite, vesuvianite, wollastonite and Ca-plagioclase and (2) a retrograde skarn stage including scheelite-bearing massive sulphide ores (pyrrhotite, chalcopyrite, tremolite-actinolite, diopside-hedenbergite) and scheelite-rich fault rocks with calcite, sericite and chlorite. The two ore stages, the mineral paragenesis and composition is like that of a reduced tungsten skarn; i.e., garnet is grossular-rich, clinopyroxene is diopside-hedenbergite. Vesuvianite contains up to 1.8 mass % fluorine. Scheelite has been studied by cathodoluminescence (CL), electron probe microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. Three types of scheelite (Scheelite 1–3) are distinguished. In short-wave UV light, all types show blue fluorescence but CL revealed internal micro-textures in scheelite grains which are dominated by oscillatory zoning. Prolonged hydrothermal activity is indicated by dissolution-replacement and overgrowth textures affecting the primary zonation and trace element composition of scheelite. The distribution of rare earth elements (REE) in Scheelite 1 in tonalite-hosted quartz veinlets shows a convex (i.e., middle REE-enriched), heavy REE-depleted pattern with negative Eu anomalies (EuA ). The evolution of REE patterns from skarn-hosted Scheelite 2 and 3 illustrates a gradation of convex REE patterns with high ΣREE and distinct negative Eu anomalies to relatively flat REE patterns with small to no EuA . Scheelite at Lienzer Schlossberg has one of the highest ΣREE+Y contents of all scheelite-bearing ore settings in the Eastern Alps but incorporates minor Mo and the least Sr. High Na and Nb contents together with the positive correlation of REE+Y vs. Na+Nb+Ta suggests that the main exchange vectors for REE incorporation in scheelite is via a combined coupled substitution mechanism. Results of this study confirm the genetic similarity with reduced tungsten skarns and highlight the tungsten potential of this area.

Quasi‐Continuous Defect Levels in Broadband Gap: A New Strategy for High‐Temperature Long Persistent Luminescence Materials

AbstractLong persistent luminescence (LPL) materials widely employed in the fields of emergency lighting and anti‐counterfeiting are mostly used at room temperature. As temperatures rise, the performance of LPL materials deteriorates dramatically, which hinders their application in in vivo imaging, high‐temperature display, and information storage. Herein, a multifunctional material LiGa5O8:Tb3+ (LGT) with green high‐temperature LPL (HT‐LPL) and blue cathodoluminescence (CL) is reported. Its LPL performance is anomalously enhanced with increasing temperature, and the duration time is more than 8 h at 423 K. With combined temperature‐dependent decay curves and thermoluminescence analyses, the unique quasi‐continuous defect levels are found in the band gap. The high‐concentration carriers in deep traps are frozen at room temperature and activated only at high temperatures, accompanied by changes in energy transfer pathways. The excellent HT‐LPL makes LGT a light‐emitting component of next‐generation smart wearable devices, as well as high‐temperature warning equipment in deep well exploration at a depth of 4500 m. The intense anti‐degradation blue CL makes it suitable for field emission displays, while the manipulable emission property makes it suitable for high‐level anti‐counterfeiting. This study fills a gap in HT‐LPL materials and opens up a new gateway for the efficient design of HT‐LPL and other multifunctional materials.

Apatite texture and composition in the Tonglushan porphyry-related skarn system, eastern China: Implications for mineral exploration

The composition of ‘indicator’ minerals is thought to provide a guide to the potential of magmatic arc systems to form porphyry Cu deposits, but whether this is also the case for endoskarn- and exoskarn-dominated systems remains unclear, despite their importance as a source of Cu, Fe and Au. In a first step to address this, we compare the texture, cathodoluminescence (CL) colour and composition of apatite between relatively fresh quartz monzodiorite (QMD) and porphyry-type-, endoskarn- and Fe-(Cu)-mineralised exoskarn components of the Tonglushan porphyry-skarn system of the Daye ore district, China. In the relatively fresh QMD, apatite luminesces yellow-green due to elevated Mn contents. However, where affected by potassic-sodic alteration, it shows green–blue CL thought to reflect partial removal of Mn and an associated increase in REE. Apatite in the endoskarn is more pervasively replaced and veined, and shows mid-blue luminescence due to relatively low Mn, Mg and Cl. The exoskarns contain apatite with variable grain shapes and navy blue-violet or bright to dark blue CL colours, caused by low Mn and elevated Ce, and with only small patches of pale yellow-green CL. Apatite is near absent in the limestone wall rocks and xenoliths and, therefore, where present in the exoskarns is interpreted to have precipitated from the same fluids as the Fe-(Cu) mineralization.Apatite CL colour and chemistry is indicative of the different styles of alteration and mineralisation in the Tonglushan system and provides insights into the composition of skarn-forming fluids. Our results offer a potentially effective method for utilising apatite as a porphyry and skarn deposit indicator mineral in a range of exploration materials including regolith and stream sediments.

Cathodoluminescence, Raman and scanning electron microscopy with energy dispersion system mapping to unravel the mineralogy and texture of an altered CaAl‐rich inclusion in Renazzo CR2 carbonaceous chondrite

AbstractAn altered fluffy type A CaAl‐rich inclusion in the CR2 Renazzo carbonaceous chondrite was examined by combined Raman, scanning electron microscopy with energy dispersion system (SEM‐EDS) and cathodoluminescence (CL) mapping. Blue CL at 450 nm and orange emission at 600 nm were related to anorthite and calcite, respectively. Raman spectra were highly fluorescent, and only the stronger peaks of anorthite, clinopyroxene and calcite were observed. Raman‐induced fluorescence emission was measured using the 632‐nm Raman laser source, up to 850 nm, and used to chart the mineral phases. A fluorescence structured peak at 690 nm, split in three subpeaks at 678, 689 and 693 nm, was found; it is likely related to the fluorescence emission of Cr3+ from a fassaitic pyroxene in anorthite. Secondary pyroxene in the Wark–Lovering rim does not show the peak at 690 nm; the different fluorescence emission from the secondary rim and the pyroxene patches within anorthite could be a marker to spot the primary pyroxene. From combined imaging, the events in the altered chondrite could be sequenced. Starting from a pristine assemblage of spinel and melilite, with little fassaite, several alteration episodes occurred. Alteration in secondary anorthite, which could be mapped by the blue CL emission at 450 nm, was followed by alkalization, with rims of sodalite and nepheline, and subsequent formation of secondary clinopyroxene, encircling the inclusion. Widespread calcite alteration, present also in the matrix between chondrules, was the last recorded event.

Parasitic p–n junctions formed at V-pit defects in p-GaN

The luminescent and recombination properties of V-pit defects in p-GaN(Mg) grown by metalorganic chemical vapor deposition (MOCVD) were studied by scanning electron microscopy (SEM) in the secondary electron, cathodoluminescence (CL), and electron beam induced current (EBIC) modes, combined with CL spectra measurements and EBIC collection efficiency measurements. Similar studies were performed on low-dislocation-density freestanding n-GaN crystals. For MOCVD p-GaN films, the SEM investigations were supplemented by capacitance–voltage, current–voltage, deep level transient spectroscopy analysis with Ni Schottky diode, and Ohmic contacts. These experiments show that V-pits in p-GaN increase the leakage current of Schottky diodes, as in n-GaN films and crystals. EBIC imaging and EBIC collection efficiency results suggest that in the region of V-pits, a parasitic p–n junction is formed. We also observe that, in V-pits, the CL spectra the contribution of the 3.2 eV defect band is strongly enhanced compared to the 3 eV blue CL band that dominates the spectra.

Multistage evolution of the Neoproterozoic “El Tarumán” gold vein-type mineralization, Dom Feliciano orogenic belt, Uruguay

Vein-type gold occurrences are found along the western margin of the Neoproterozoic Dom Feliciano Belt (Uruguay) and its Archean to Proterozoic basement. The “El Tarumán” gold prospect is related to quartz veins hosted in dolomitic marble, which is part of the Cebollati Complex, metamorphosed in amphibolite facies. The quartz veins formed in fold hinges and sheared marble bands in a transpressive regime. Their orientation coincides with the Brasiliano structural grain, striking mostly NNE-SSW. Pyrite is the most important ore mineral, besides minor galena, chalcopyrite, and sphalerite, and accessory enargite, chalcocite and tennantite. The oxidation of sulfides produced free gold besides malachite.In our study, we combined fluid inclusion data with microstructures, which represent successive alteration stages after hydrothermal quartz mineralization and are made visible by cathodoluminescence (CL)-microscopy. In this way, the fluid evolution during the main mineralization and subsequent cooling could be constrained. The vein mineralization was associated with post-collisional magmatism and hydrothermal fluid circulation at ca. 500–550 °C/3 kbar, postdating the peak of metamorphism. The mineralizing fluid with an estimated composition of H2O(55) CO2(40) NaCl(5) was trapped as primary fluid inclusions in non-deformed quartz (T0) showing blue CL. Alteration structures (T1-T4) are marked by quartz showing brown and reddish CL hosting different types of fluid inclusions, and are characterized by (T1) a diffusive intragranular mosaic structure (subgrains), most likely related to minor ductile shearing, (T2) grain boundaries which formed as a result of dynamic recrystallization (secondary grain growth), (T3) shear bands of fine-grained quartz, and (T4) healed microfractures. The fluid inclusions trapped in these structures represent retrograde fluids characterized by a systematic loss of CO2 because of carbonation, slightly increasing salinity and the introduction of CaCl2. The latter solutes were mainly trapped around the quartz brittle-ductile transition zone between 350 and 300 °C/2.5–3 kbar (T1), and 300-260 °C/2–2.5 kbar (T2), together with the precipitation of pyrite. This shows that the sulfides formed by the interaction of cooling hydrothermal fluids and the host rock. The CaCl2/NaCl ratio for the inclusions in the T2-structures is ca. 0.65 at maximum. Late shear bands of fine-grained quartz (T3) are free of fluid inclusions. The latest fluids preserved in the quartz veins were trapped in healed microfractures below ca. 280 °C and represent the influx of low salinity (6–7 wt %) NaCl-bearing solutions (T4).The structural data and high fluid trapping temperatures indicate that the veins host an orogenic gold mineralization associated with magmatic hydrothermal fluids. The finding of an Ediacaran K–Ar cooling age of 592.8 ± 8.7 Ma for muscovite in the veins is consistent with regional sinistral shearing and strong basement reworking during the Neoproterozoic Brasiliano Orogeny.

Understanding the evolution of magmatic-hydrothermal systems based on microtextural relationships, fluid inclusion petrography, and quartz solubility constraints: insights into the formation of the Yulong Cu-Mo porphyry deposit, eastern Tibetan Plateau, China

The evolution of the magmatic-hydrothermal system that formed the Eocene Yulong Cu-Mo porphyry deposit of the eastern Tibetan Plateau, China, is reconstructed based on the study of the sequence of stockwork vein sets showing systematic crosscutting relationships in hand specimen. Early A veins associated with potassic alteration of the porphyritic host are composed of vitreous quartz that is extensively recrystallized and has a dark blue cathodoluminescence. Fluid inclusions contained in the quartz have been affected by post-entrapment modification. Some of the A veins were reopened and contain ribbons of microscopic molybdenite flakes. Formation of the molybdenite was associated with recrystallization of the earlier formed quartz and concomitant with the development of a dark purple to brownish cathodoluminescence signature. Reopening of the early veins also resulted in the formation of AB veins containing euhedral quartz crystals that contain encapsulated molybdenite flakes and are intergrown with coarse laths of molybdenite. These euhedral quartz crystals showing a dark purple to brownish cathodoluminescence host vapor-rich, intermediate-density fluid inclusions as well as hypersaline liquid and vapor-rich fluid inclusions, indicating that fluid immiscibility at hydrostatic pressure conditions occurred during crystal growth. Later, C veins that crosscut and commonly reopen the earlier A and AB veins lack quartz as a gangue mineral and consist entirely of chalcopyrite and pyrite with minor molybdenite. Sulfide formation was accompanied by chlorite or sericite alteration of the wall rocks. Late D veins containing quartz and pyrite with associated sericitic alteration of the porphyritic wall rocks crosscut all earlier vein types. Only minor amounts of molybdenite and chalcopyrite are present. Euhedral quartz crystals in the D veins contain liquid-rich fluid inclusions that have not been affected by post-entrapment modification. The results of this study indicate that Mo and Cu mineralization at Yulong was introduced by single-phase, intermediate-density magmatic-hydrothermal fluids as the porphyry system was transitioning from ductile to brittle conditions. The bulk of the Mo endowment predated Cu mineralization and formed during the change from lithostatic to hydrostatic conditions and associated immiscibility of the magmatic-hydrothermal fluids. Chalcopyrite precipitation followed as the single-phase, intermediate-density magmatic-hydrothermal fluids was escaping into the hydrostatic-pressured regime. Cooling of the magmatic-hydrothermal fluids appears to have been the principal control on metal precipitation.

Cathodoluminescence degradation of Y2O3:Dy3+ nanophosphor for field emission displays

Cathodoluminescence (CL) degradation of Y2O3:Dy3+ nanophosphors prepared by the solution combustion method was explored for feasible applications in low voltage field emission displays (FEDs). Oxide materials are excellent candidates for FED fabrication due to their high melting points, chemical and radiation stability with long lifetimes, high color purity, and being environmentally friendly. Auger electron spectroscopy (AES) and x-ray photoelectron spectroscopy (XPS) were used to monitor changes in the surface chemical composition and correlation fit with CL degradation. AES and CL spectroscopy (2 keV energy electrons and with a beam current of 15 μA) measurements were done in high vacuum (1.5 × 10−8 Torr) and oxygen pressures of 1 × 10−7 and 5 × 10−7 Torr. The Y2O3:Dy3+ nanophosphor showed strong yellow (572 nm) and relatively weaker blue (492 nm) CL emissions. These CL emissions increased as carbon (C) was depleted from the surface, and then it slightly decreased at a high electron dose in both the vacuum and oxygen atmospheres, for electron doses up to about 690 C/cm2. The C was depleted from the surface due to electron stimulated reactions. No significant change in the chemical state of Y 3d was observed with XPS high resolution spectra for the postirradiation sample. The change in the CL intensity was, therefore, attributed to the depletion of C from the surface.

Agate mineralization in spilitized Permian volcanics from “Borówno” quarry (Lower Silesia, Poland) – microtextural, mineralogical, and geochemical constraints

Two forms of silica mineralization, i.e.: (1) vein agates and (2) moss agates, were encountered for the first time within spilitized (albite-rich) alkali-basalts from the upper parts of Borówno quarry (Intra-Sudetic Basin). Vein agates consist predominately of length-fast chalcedony evolving into strongly-zoned prismatic quartz with a distinctive blue cathodoluminescence. They exhibit the abundance of microtextures typical of epithermal vein systems (i.e. pseudo-bladed, flamboyant/feathery, jigsaw puzzle/mosaic, and Bambauer quartz), but also comprise numerous solid inclusions such as sulphides (pyrite, marcasite, chalcopyrite, and chalcocite), sulphates (barite), carbonates (calcite, dolomite), carbonaceous material, and hematite. The formation of vein agates was marked by strong variations in physicochemical conditions (pH, silica content) of SiO2-bearing fluids and recrystallization of metastable silica phases (i.e. moganite), coupled with the local replacement of pre-existing sulphates and/or carbonates by silica during boiling-related conditions. Their LREE-enriched rare-earth patterns with positive Eu anomaly invoke the close relationship between host rocks alterations (spilitization) and origin of SiO2-rich fluids. Conversely, moss agates have formed as a result of a spherical growth of siliceous phases within vesicles and contain numerous mineral inclusions of hematite, goethite, anatase, as well as ore-related phases (mottramite and dickite). The examination of their surface micro-morphology showed a strong age-related maturation marked by the development of stacked silica plates (plate-edge-like structure). The botryoidal-shaped, white-coloured, and Al-enriched outermost layer of these agates possibly reflects a rapid deposition of the initial silica gel onto the cavity walls. The HREE-enriched rare-earth patterns of the moss agates, combined with the presence of positive Eu and Ce anomalies, suggest their parental SiO2-rich fluids could be derived from multiple sources (e.g. volcanics mesostasis and/or meteoric waters). The fluids responsible for the formation of agate mineralization within alkali-basalts in Borówno could be derived from syn- or post- alterations of their host rocks.

Quartz and zircon decoupling in sandstone: Petrography and quartz cathodoluminescence of the Early Triassic continental Buntsandstein Group in Germany

AbstractThis study illustrates how decoupling of quartz and zircon can be used advantageously in provenance research. Thirty‐eight fine‐grained to coarse‐grained arkose samples of the Early Triassic intracontinental Buntsandstein Group from the Central European Basin in Germany were analysed for their petrography and 1200 grains in 23 of these for their detrital quartz cathodoluminescence characteristics. The samples represent the Hessian and Thuringian sub‐basins and the Eichsfeld–Altmark Swell separating them. The Hessian Sub‐basin includes more metamorphic lithoclasts with a larger content of plutonic grains than are found further east in the Thuringian Sub‐basin. More than 90% of the detrital quartz from the eastern Thuringian Sub‐basin produce medium to bright blue cathodoluminescence colours and corresponding spectra that are typical for igneous or high‐temperature metamorphic origin. Differently, the quartz from the Hessian Sub‐basin mostly luminesces brown and dark to medium blue, typical for a low‐temperature metamorphic origin. Quartz from the Eichsfeld–Altmark Swell and the western Thuringian Sub‐basin is a mixture between these origins. The quartz indicates different catchments for the sub‐basins, possibly the Bohemian Massif and the Massif Central, with converging transport routes on and close to the eastern fringe of the swell. Taking published zircon data from the same samples into account, light mineral‐zircon grain‐size shifts are up to 2 Φ units. That can be explained by mineral decoupling due to different transport modes for quartz and zircon and different zircon‐size availability in the source areas, exaggerated by combined aqueous–aeolian transport, as well as sample preparation‐induced sorting. This study concludes that submerged highs significantly can influence continental sediment transport. Hence, vast, flat continental areas with submerged morphological highs and a seemingly straightforward transportation pattern may be more complex than expected. The results also illustrate that analysis of detritus that has been affected by different dominating transport modes, and further sorting during sampling and preparation can reveal additional source information.

Deciphering Silicification Pathways of Fossil Forests: Case Studies from the Late Paleozoic of Central Europe

The occurrence and formation of silicified wood from five late Paleozoic basins in Central Europe was investigated. Fossil wood from diverse geological settings was studied using field observations, taphonomic determinations as well as mineralogical analyses (polarizing microscopy, cathodoluminescence (CL) microscopy and spectroscopy). The results indicate that silicification is either a monophase or multiphase process under varying physico-chemical conditions. In particular, CL studies revealed complex processes of silica accumulation and crystallization. The CL characteristics of quartz phases in silicified wood can mostly be related to blue (390 and 440 nm), yellow (580 nm), and red (650 nm) emission bands, which may appear in different combinations and varying intensity ratios. Yellow CL is typical for initial silicification, reflecting quick precipitation under oxygen-deficient conditions caused by initial decay of the organic material. Blue CL is predominantly of secondary origin, resulting from replacement of precursor phases by a secondary hydrothermal quartz generation or subsequent silicification of wood. The red CL can be related to a lattice defect (non-bridging oxygen hole center—NBOHC).

Diagenetic evolution of the upper Devonian phosphorites, Alborz Mountain Range, northern Iran

The upper Devonian, mixed siliciclastic‑carbonate stratigraphic succession of the Geirud Formation in the Alborz Mountain Range, north of Iran, hosts numerous phosphorites and phosphatic rocks. These phosphorites, which represent one of the most globally important deposits in the Devonian, have gained little attention regarding their genesis and diagenetic evolution. This study focuses mainly on the post-depositional changes that occurred during shallow to deep burial diagenetic evolution and subaerial weathering of the Geirud phosphorites. The phosphorites consist of phosphatic massive mudclasts, detritus-rich lithoclasts, bioclasts and bones formed by several stages of phosphogenesis and erosion, reworking, winnowing and condensation associated with Famennian sea level changes. The phosphatic clasts consist of early diagenetic, poorly crystalline, carbonate fluorapatite (CFA) and pyrite cementing detrital quartz, illite, muscovite, rutile and zircon. Phosphatic clasts are intensely compacted with sutured grain contacts, along which dissolution and reprecipitation of chemically-refined, well crystalline CFA with a bright blue cathodoluminescence and illite occurred during deep burial diagenesis. Similarly, quartz shows deformation planar features; overgrowth cement was developed as a result of pressure dissolution in phosphatic sandstones, followed by precipitation of ferroan dolomite, ankerite and chlorite in secondary porosity. Subaerial weathering led to oxidation of pyrite and generation of acidic pH condition, under which Ca and P from phosphates, Fe and S from pyrite, Fe, Ca, Mg and Mn from ferroan carbonates and Al and Si from aluminosilicates were released to form goethite, psilomelane, calcite, gypsum and crandallite.The PAAS-normalized rare earth elements (REEs) show bell-shaped patterns with middle (REEs) enrichment, positive Eu anomaly and a weak negative Ce anomaly. This implies recrystallization of CFA in phosphorites and phosphatic rocks during deep burial diagenesis, deviating from the modern seawater-like REE patterns. In this regard, deep burial diagenesis affecting the upper Devonian Geirud phosphorites is possibly a common process in the Proterozoic-Paleozoic phosphorites in northern Iran and elsewhere in the world.

Multi-Stage Evolution of Gold-Bearing Hydrothermal Quartz Veins at the Mokrsko Gold Deposit (Czech Republic) Based on Cathodoluminescence, Spectroscopic, and Trace Elements Analyses

We performed a detailed analysis of hydrothermal quartz at the Mokrsko gold deposit (Čelina, Mokrsko-East, and Mokrsko-West deposits). Twenty-one samples were studied by scanning electron microscopy cathodoluminescence (CL) imagining, CL emission spectra and trace elements were measured on six selected samples. Four quartz growth generations Q1 to Q4 were described. Homogeneous early blue CL Q1 with initial emission spectra at 380 and 500 nm was observed at the Čelina deposit with typical titanium concentrations in the range of 20–50 ppm. Hydrothermal quartz at Mokrsko-West, which also includes early Q1, late subhedral faces of yellow CL Q2, and microfissures of greenish CL Q3 (both 570 nm), is characterized by titanium depletion. The titanium concentration is comparable to previous studies of crystallization temperatures proving titanium concentration in quartz as a good geothermal indicator. Q4, developed in microfissures only at Čelina, has no visual CL effect. Mokrsko-West is specific in comparison to Mokrsko-East and Čelina by germanium enrichments in hydrothermal quartz (up to 17 ppm) and the presence of fluorite. Tectonic (sheeted veinlets system, regional tectonic setting) and geochemical (germanium in quartz, the presence of fluorite) characteristics of the quartz veins link the late mineralization stages at the Mokrsko-West deposit to the temporally related Blatná intrusive suite.

Cathodoluminescence (CL) Characteristics of Quartz from Different Metamorphic Rocks within the Kaoko Belt (Namibia)

Quartz of metamorphic rocks from the Kaoko belt (Namibia) representing metamorphic zones from greenshist to granulite facies were investigated by cathodoluminescence (CL) microscopy and spectroscopy to characterize their CL properties. The samples cover P-T conditions from the garnet zone (500 ± 30 °C, 9 ± 1 kbar) up to the garnet-cordierite-sillimanite-K-feldspar zone (750 ± 30 °C, 4.0–5.5 kbar). Quartz from 10 different localities and metamorphic environments exclusively exhibits blue CL. The observed CL colors and spectra seem to be more or less independent of the metamorphic grade of the host rocks, but are determined by the regional geological conditions. Quartz from different localities of the garnet-cordierite-sillimanite-K-feldspar zone shows a dominant 450 nm emission band similar to quartz from igneous rocks, which might be related to recrystallization processes. In contrast, quartz from different metamorphic zones in the western part of the central Kaoko zone (garnet, staurolite, kyanite, and kyanite-sillimanite-muscovite zone) is characterized by a heterogeneous blue-green CL and a dominant 500 nm emission band that strongly decreases in intensity under electron irradiation. Such CL characteristics are typical for quartz of pegmatitic and/or hydrothermal origin and indicate the participation of fluids during neoformation of quartz during metamorphism.

Photo- and cathodoluminescence of Eu3+ or Tb3+ doped CaZrO3 films prepared by pulsed laser deposition

Luminescent films of Eu3+ or Tb3+ doped CaZrO3 were epitaxially grown on SrTiO3 or LaAlO3 (001) single crystal substrates by pulsed laser deposition (PLD). They showed a high transmittance in the visible region and a smooth surface. Uniform red photoluminescence (PL) was observed from Eu3+ 5% doped films, and blue and green PL was observed from Tb3+ 0.5% and 5% doped films, respectively. These PL spectra of the films turned out to be very similar to those of the powder samples. Practically, it has to be noticed the use of a LaAlO3 substrate is necessary for intense blue luminescence for Tb3+ 0.5% doped films to avoid optical absorption of emitted light by the SrTiO3 substrate. The cathodoluminescence (CL) spectra of the red and green luminescent films were almost the same as those PL spectra. In contrast, blue CL was significantly enhanced in CL compared to PL. This was attributed to the shorter lifetime of the 5D3-7FJ transitions and many excited electron-hole pairs, which were generated rapidly on high energy electron irradiation.

Integrated methodology for determining provenance of detrital quartz using optical petrographic microscopy and cathodoluminescence (CL) properties

The provenance of detrital quartz is a useful predictor in frontier basin sandstone reservoirs of the availability of coarse-grained quartz grains of plutonic or high grade metamorphic origin. The standard approach is to use scanning electron microscope (SEM) panchromatic cathodoluminescence (CL) imagery and observations from an optical petrographic microscope. We describe a work flow, modified from previous literature proposals, to determine quartz provenance in detrital grains using optical petrographic microscopy and CL properties from both a hot-cathode cathodoluminescence microscope attachment (HCMA) and panchromatic SEM-CL. HCMA analysis permits better discrimination of different types of metamorphic quartz. This method is applied to a Middle Jurassic to Lower Cretaceous section in the Bandol-1 wildcat well, located in the Laurentian sub-basin south of Newfoundland. Two types of high-grade metamorphic quartz are distinguished, one with low luminescence as described in previous literature and one with medium blue CL colour and a moderate colour shift that is also known from granulite in the hinterland. Three phases of detrital supply are identified, suggesting progressive unroofing of higher grade metamorphic sources through the middle Jurassic and major input of plutonic quartz in the early Cretaceous.

Formational Conditions For the Binntal Emerald Occurrence, Valais, Switzerland: Fluid Inclusion, Chemical Composition, and Stable Isotope Studies

Abstract Emerald from the Binntal occurrence in the Canton of Valais in Switzerland has been studied to determine its chemical zonation, stable isotopic signatures, depositional-fluid characteristics, pressure-temperature emplacement conditions, and formational model. The emerald is vanadium-rich, with optical and blue cathodoluminescence zoning related to chemical variations, primarily in V 2 O 3 concentrations. The hydrogen isotope signature of the emerald channel fluids is unique and in agreement with previously identified high-altitude (deuterium-depleted) Alpine-age meteoric fluids. Field studies, fluid inclusion analyses, and oxygen isotope thermometry are consistent with a metamorphic formational model for the Binntal emerald at temperatures and hydrostatic pressures ranging from 200 to 400 °C and 100 to 250 Mpa, respectively. This corresponds to formational depths on the order of 4 to 9 km and fluids consistent with a 10–20 Ma CO 2 -dominant fluid with approximate mole percentages of 84.0, 11.9, 1.5, 1.3, 0.3, and 0.5 for CO 2 , H 2 O, CH 4 , N 2 , H 2 S, and NaCl, respectively.

Cathodoluminescence color zonation in the Antarctic meteorite (enstatite chondrite) of Yamato 86004

AbstractEnstatite in Yamato 86004 classified as EH melt rock shows cathodoluminescence (CL) zonation as arranged in a concentric pattern from within outward blue, light blue, red and non-CL areas (fusion crust). The zonation observed in the meteorite results from different distribution ratio of the enstatite with various CL colors. CL spectra of the enstatite have two broad emission bands at around 400 nm in the blue region and at around 670 nm in a red region. The emission components obtained by a spectral deconvolution can be assigned to three defect centers (2.73, 3.13–3.15 and 3.77 eV) in a blue region and to impurity centers of Cr3+ion (1.71 eV) and Mn2+ion (1.86–1.91 eV) in a red region. According to the CL related to structural defects in the enstatite, blue-CL enstatite might be originally formed from the melt by a quenching from the melt on the surface of parent body. The enstatite with light blue and red CL might be thermally altered from blue-CL enstatite with phase transitions during a flash heating when the meteorite passed through the atmosphere. Therefore, the color CL zonation reflects a thermal history recorded in the meteorite.