Cathodoluminescence of Rare Earth Doped Zircons. I. Their Possible Use as Reference Materials

Synthetic zircon crystals (ZrSiO4), undoped and doped with Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, were grown from a flux consisting of a mixture of Li2MoO4 and MoO3 heated to 1125°C and then cooled to 750°C. The cathodoluminescence (CL) spectra of these zircons were analyzed at room-temperature and near liquid nitrogen temperature with a CL spectrometer attached to a scanning electron microscope (SEM). This study highlights the complexity of the intrinsic emission band extending from 200 to 500 nm. The relative intensities of the major emission band centered at 230 nm (5.4 eV) and peaks of less energy were found to depend upon the crystallographic orientation of the crystals. Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+ and Tm3+-doped zircons display sharp emission peaks being characteristic of the doping rare-earth element (REE). These lines are frequently multiplets but only the average position of the peaks are reported because of the instrumental conditions used in this study. The CL intensities of the intrinsic and extrinsic features were found to depend on the crystal orientation, and numerous experimental factors such as the electron beam energy and the beam current density

Cathodoluminescence of Rare Earth Doped Zircons. II. Relationship Between the Distribution of the Doping Elements and the Contrasts of Images

Cathodoluminescence (CL) color photographs using an optical CL microscope with a cold cathode electron gun are compared with non-spectrally resolved (polychromatic) and selected wavelength CL images obtained by means of a scanning electron microscope equipped with a CL spectrometer. It is the aim of this paper to show how the interpretation of the contrasts of CL images depends on the knowledge of the CL photon energy distributions participating to the observed contrasts as well as the matrix effects modifying the number of emitted photons compared to that of generated photons. It is shown that the impurities different from the rare earth elements (REE) activators are responsible for charge trapping mechanisms leading to the development of internal electric fields modifying the energy and spatial distribution of the electrons within the insulators and consequently modifying the relative intensities of the intrinsic (host lattice) emission and characteristic emission of a REE activator. In addition, the mechanisms of production of photons must be better understood before trying to express the CL intensity of a monochromatic line as a function of the corresponding REE activator

Cathodoluminescence Applied to the Microcharacterization of Mineral Materials: A Present Status in Experimentation and Interpretation

Experimentation and interpretation of cathodoluminescence (CL) microscopy and spectroscopy applied to the microcharacterization of material minerals are reviewed. The origins of the intrinsic (host lattice) and extrinsic (impurities) luminescence emissions in crystals are briefly discussed. Merits and limitations of the available techniques are illustrated. CL emission changes as a function of the incident electron dose are illustrated for the case of natural quartz and sphalerite (ZnS) crystals. These effects are discussed in terms of the development of bulk charging, production of heat, diffusion of impurities, and creation of lattice defects induced by the incident ionizing particles. Although CL emission is mostly extrinsic in origin there is no general rule for identifying the nature of impurities from the CL emission spectra of minerals. However there is potential for using CL spectroscopy for trace element analysis as presented for the case of minerals containing rare-earth luminescent ions. The CL emission is a signature of the crystal-chemistry properties of minerals and hence contains potential genetic information. Some of the applications of CL emissions in the geosciences are summarized

A hidden alkaline and carbonatite province of early carboniferous age in northeast Poland: Zircon U-Pb and pyrrhotite Re-Os geochronology

Extensive geophysical investigations in NE Poland in the 1950s and 1960s led to the discovery of an alkaline and carbonatite magmatic province buried under thick (600-800 m) Meso-Cenozoic cover north of the Trans-European Suture Zone, or Tornquist Line. Drilling focused on geophysical anomalies identified three intrusions in the Paleoproterozoic metasedimentary and metavolcanic rocks of the Mazowsze Domain: the Pisz gabbro-syenite massif, the Ełk syenite massif, and the small, differentiated Tajno body consisting of clinopyroxenite cumulates and syenites crosscut by carbonatite veins. Emplacement ages for these intrusions have been obtained by (1) zircon U-Pb geochronology on a gabbro from Pisz, a syenite from Ełk, and an albitite from Tajno and (2) a Re-Os model age for pyrrhotite from a Tajno carbonatite. The ages measured by both methods fall in the narrow range 354-345 Ma (Early Carboniferous: Tournaisian). This is slightly younger than the Late Devonian (380-360 Ma) Kola Peninsula alkaline and carbonatite province (20 intrusions) of NW Russia and Karelia but is of comparable age to the first manifestations of the long-lasting (~100 m.yr.) Carboniferous to Permian magmatic event (360-250 Ma) manifest in northern Europe (from the British Isles to southern Scandinavia, the North Sea, and northern Germany) in the foreland of the Variscan orogeny (in the so-called West European Carboniferous Basin) and the East European Craton

Gem corundum deposits in Vietnam

Since 1983, gem-quality rubies have been recovered from the Luc Yen and Quy Chau mining areas in northern Vietnam. Since 1991, 'basaltic'-type blue-green-yellow ('BGY') sapphires have been mined in southern Vietnam. This article briefly reviews the history and geology of these different areas and shows the importance of marble and basalt-type deposits. Other types of corundum occurrences are found in amphibolite, pegmatite, gneiss and metasomatite. The gemmological, chemical and isotopic characteristics of these different types of corundum are described.<br /> The most notable features of rubies contained in marbles are that many crystals have blue colour zones, and inclusions of rutile, anhydrite and salts. The primary fluid inclusions are composed of carbon dioxide and hydrogen sulphide with native sulphur and diaspore daughter minerals. Sapphires from placers in basalts are characterized by inclusions of columbite, pyrochlore and baddeleyite. The trace element contents of corundums allow distinction of rubies in marbles from sapphires in basalts and metamorphic rocks. Rubies have high chromium (0.54<Cr<sub>2</sub>O<sub>3</sub><O.66 wt.%)and low iron (0.01<FeO<0.07 wt.%) contents. The geological origin of Vietnam corundums can be clearly determined from the isotopic composition of their structural oxygen, i.e. δ 18O = 21.0 ± 0.9% for rubies in marbles and δ 18O = 6.6 ± 0.4% for sapphires in basalts

Osmium isotope systematics of the Proterozoic and Phanerozoic ophiolitic chromitites : in situ ion probe analysis of primary Os-rich PGM

Author Posting. © Elsevier B.V., 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 245 (2006): 777-791, doi:10.1016/j.epsl.2006.03.021.In-situ 187Os/188Os ratios are determined on Os-rich platinum-group minerals in podiform chromitites both in the Proterozoic ophiolite, Eastern Desert, Egypt, and in the Phanerozoic Oman ophiolite. Because they have very low Re/Os, these primary minerals reflect the initial 187Os/188Os ratios of their parental magmas. The platinum-group minerals (PGM) in the central Eastern Desert chromitites exhibit sub-chondritic to chondritic 187Os/188Os ratios, 0.1226 on average, which is lower than the primitive upper mantle evolution trend of a comparable age. Those of the southern Eastern Desert chromitites have more radiogenic Os, with supra-chondritic 187Os/188Os ratio of about 0.1293 on average, which could be due to crustal contamination. The three chromitite types in the northern part of the Oman ophiolite are almost indistinguishable in terms of their 187Os/188Os ratios; they have overlapping values ranging from sub-chondritic to supra-chondritic ratios. The PGE-rich, mantle chromitite samples have a wide range of 187Os/188Os ratio from 0.1230 up to 0.1376, with an average of 0.1299. The values of the PGE-poor mantle chromitites overlap in their 187Os/188Os ratios with PGE-rich chromites, but are less variable and have a significantly higher average ratio. The Moho transition zone (MTZ) chromitites are highly variable in the 187Os/188Os ratio, ranging from 0.1208 up to 0.1459. The wide range of 187Os/188Os ratios, from 0.1192 to 0.1459, in platinum-group minerals in Egyptian and Oman ophiolites can be attributed to the diversity of origin of their podiform chromitites. The Os-isotope data combined with spinel chemistry indicate that the way involved in podiform chromitite formation was not substantially different between the Proterozoic ophiolite of Egypt and the Phanerozoic ophiolite in northern Oman. The Os-isotope compositions of the mantle chromitites in the Proterozoic ophiolite of Egypt clearly suggest crustal contamination. The heterogeneity of 187Os/188Os ratios combined with the spinel chemistry and high PGE contents of the PGE-rich chromitite in the Oman ophiolite may give reliable evidence for high degree partial melting at a supra-subduction zone setting. Crustal contamination from the subducted slab, and assimilation of previously altered, lower crustal gabbro, may have contributed to the high Cr# spinel and radiogenic Os characteristics in chromitite formed in the mantle section and along the Moho transition zone, respectively.Kelemen and Hanghøj were supported in this project by US National Science Foundation grants OCE-9819666 and OCE-0118572

Contrasting styles of (U)HP rock exhumation along the Cenozoic Adria-Europe plate boundary (Western Alps, Calabria, Corsica)

Since the first discovery of ultrahigh pressure (UHP) rocks 30 years ago in the Western Alps, the mechanisms for exhumation of (U)HP terranes worldwide are still debated. In the western Mediterranean, the presently accepted model of synconvergent exhumation (e.g., the channel-flow model) is in conflict with parts of the geologic record. We synthesize regional geologic data and present alternative exhumation mechanisms that consider the role of divergence within subduction zones. These mechanisms, i.e., (i) the motion of the upper plate away from the trench and (ii) the rollback of the lower plate, are discussed in detail with particular reference to the Cenozoic Adria-Europe plate boundary, and along three different transects (Western Alps, Calabria-Sardinia, and Corsica-Northern Apennines). In the Western Alps, (U)HP rocks were exhumed from the greatest depth at the rear of the accretionary wedge during motion of the upper plate away from the trench. Exhumation was extremely fast, and associated with very low geothermal gradients. In Calabria, HP rocks were exhumed from shallower depths and at lower rates during rollback of the Adriatic plate, with repeated exhumation pulses progressively younging toward the foreland. Both mechanisms were active to create boundary divergence along the Corsica-Northern Apennines transect, where European southeastward subduction was progressively replaced along strike by Adriatic northwestward subduction. The tectonic scenario depicted for the Western Alps trench during Eocene exhumation of (U)HP rocks correlates well with present-day eastern Papua New Guinea, which is presented as a modern analog of the Paleogene Adria-Europe plate boundary

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu–PGE–Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190–700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu–Ni–PGE sulfides which require very high R factors, and settling of sulfide liquids