Zircon geochemistry and U–Pb age at rare metal deposits of syenite in the Ukrainian Shield

The distribution of rare and rare earth elements in zircon at the Yastrebets, Azov (Zr–REE–Y), and Perzhan (Be) rare metal deposits of the Ukrainian Shield was studied. Additional evidence for magmatic genesis of these deposits is obtained: unaltered zircon is characterized by a magmatic REE distribution spectrum with a somewhat higher δ¹⁸O value than that of the mantle (6.6‰ on average). The final formation stage of the deposit was marked by predominance of fluids enriched in Y, REE, Nb, and heavy oxygen, resulting in anomalous geochemical characteristics of zircon rims and alteration zones (up to 81500 Y ppm, over 10300 ppm Nb, and 13.9‰ δ¹⁸O). The age of zircon formed in ore-bearing Yastrebets and Azov nonnepheline syenite deposits was estimated at ~1770 Ma (U–Pb, SHRIMP-II).     

Geochemical characterization of zoned zircon from Wadi Abu Rusheid psammitic gneiss, south Eastern Desert, Egypt

A unique zircon was studied in the gneiss samples collected from the Wadi Abu Rusheid psammitic gneiss using electron scanning microscope and electron probe microanalyses. This zircon can be categorized into two types according to the texture and trace element content: (l) magmatic zircon slightly enriched in HfO₂ with ordinary zone. (2) Overgrowths of zircon occur as two species, the first species being highly enriched in HfO₂ with irregular zoning. The second species is highly enriched in HfO₂ forming a rim around the second species with a very sharp thinner boundary. The first type shows a distinct oscillatory internal zoning pattern without change in shape of this zone and has conspicuous inclusion-free zircon overgrowths with distinct poor concentrations in Y, Hf, Th, U, Nb, and Ta in both rim and core. The second type shows two species, the first one displays distinct irregular interval zoning and irregular overgrowth with abrupt change in composition of these zones with distinct enrichment in Y, Hf, Th, U, Nb, and Ta in the rim relative to the core. The second species is forming a rim around the first species also with distinct enrichment in Y, Hf, Th, U, Nb, and Ta content. These indicate that two events (crystallization environment) have played an important role in the formation of this zircon and largely reflect differences in whole-rock trace element contents between the successive generations of this zircon. The first event is believed to be of magmatic origin giving rise to normal composition of magmatic zircon. The second event shows an intense successive process of metasomatic activity during the formation of the Abu Rusheid radioactive gneiss. Electron microprobe analysis indicates that oscillatory zoned zircon shows poor content of Y, Hf, Th, U, Nb, Ta, and rare earth elements (REE) in the rim and core, while overgrowths of zircon are slightly enriched by these elements. Also, these analyses indicate that the Abu Rusheid psammitic gneiss has been significantly enriched by the thorite mineral (Th content up to 54.72% ThO₂) and columbite-bearing minerals (Nb content up to 64.74% Nb₂O₅, Ta content up to 9.32% Ta2O₅). The poor content of REE in overgrowths of zircon indicates mobilization of REE during the metamorphism processes of gneiss.     

Zircon from the East Orebody of the Bayan Obo Fe–Nb–REE deposit,China, and SHRIMP ages for carbonatite-related magmatism and REE mineralization events

Extremely U-depleted (<1 ppm) zircons from H8 banded ores in the East Orebody of the Bayan Obo REE–Nb–Fe deposit are presented, with mineral compositions, textures, ²³²Th–²⁰⁸Pb SHRIMP ages and petrological context. Cores of East Orebody zircon contain up to 7 wt% HfO₂ and are zoned, depicting bipyramidal crystal forms. A distinct generation of patchy, epitaxial rim zircon, similarly depleted in U, is intergrown with rare earth ore minerals (bastnäsite, parisite, monazite). Overprinting aegirine textures indicate paragenetically late, reactive Na-rich fluids. Chondrite-normalized REE patterns without Eu anomalies match closely with those from the Mud Tank and Kovdor carbonatitic zircons. Increased HREE in rims ((Lu/Gd)_N 43–112) relative to cores ((Lu/Gd)_N 6–7.5) and the localized presence of xenotime are attributable to reactive, mineralizing fluid compositions enriched in Y, REE and P. Cathodoluminescence further reveals HREE fractionation in rims, evidenced by a narrow-band Er³⁺ emission at 405 nm. The extreme depletion of U in core and rim zircon is characteristic for this mineral deposit and is indicative of a persistent common source. U depletion is also a characteristic for zircons from carbonatitic or kimberlitic systems. ²³²Th–²⁰⁸Pb (SHRIMP II) geochronological data reveal the age of zircon cores as 1,325 ± 60 Ma and a rim-alteration event as 455.6 ± 28.27 Ma. The combined findings are consistent with a protolithic igneous origin for zircon cores, from a period of intrusive, alkaline–carbonatitic magmatism. Fluid processes responsible for the REE–Nb mineralizations affected zircon rim growth and degradation during the widely reported Caledonian events, providing a new example in a localized context of HREE enrichment processes.     

Origin of zircon in jadeitite from the Nishisonogi metamorphic rocks,Kyushu, Japan

On the basis of internal structures, laser ablation U–Pb ages and trace element compositions, the origin of zircon in jadeitite in the Nishisonogi metamorphic rocks was examined. The zircon comprises euhedral zoned cores overgrown by euhedral rims. The cores contain inclusions of muscovite, quartz, albite and possibly K‐feldspar, yield ²³⁸U–²⁰⁶Pb ages of 126 ± 6 Ma (±2 SD, n = 45, MSWD = 1.0), and have Th/U ratios of 0.48–1.64. The rims contain inclusions of jadeite, yield ²³⁸U–²⁰⁶Pb ages of 84 ± 6 Ma (±2 SD, n = 14, MSWD = 1.1), and have Th/U ratios of <0.06. The cores are richer in Y, Th, Ti and rare earth elements (REEs), but the rims are richer in Hf and U. Chondrite‐normalized REE patterns of the cores indicate higher Sm_N/La_N ratios, lower Yb_N/Gd_N ratios and larger positive Ce anomalies compared with those of the rims. Thus, the cores and rims have different ²³⁸U–²⁰⁶Pb ages and trace element compositions, suggesting two stages of zircon growth. Although the ²³⁸U–²⁰⁶Pb ages of the rims are consistent with the reported ⁴⁰Ar/³⁹Ar spot‐fusion ages of matrix muscovite in the jadeitite, the ²³⁸U–²⁰⁶Pb ages of the cores are older. The mineral inclusions and high Th/U ratios in the cores are best explained by crystallization from felsic magma. Therefore, the cores are considered relicts from igneous precursor rocks. The rims surrounding the inherited cores possibly precipitated from aqueous fluids during jadeitite formation. The elevated U concentrations in the rims suggest that infiltration of external fluids was responsible for the precipitation. This study provides an example of jadeitite formation by metasomatic replacement of a protolith.     

In situ analyses of micas in the Yashan granite,South China: Constraints on magmatic and hydrothermal evolutions of W and Ta–Nb bearing granites

Most rare-metal granites in South China host major W deposits with few or without Ta–Nb mineralization. However, the Yashan granitic pluton, located in the Yichun area of western Jiangxi province, South China, hosts a major Nb–Ta deposit with minor W mineralization. It is thus important for understanding the diversity of W and Nb–Ta mineralization associated with rare-metal granites. The Yashan pluton consists of multi-stage intrusive units, including the protolithionite (-muscovite) granite, Li-mica granite and topaz–lepidolite granite from the early to late stages. Bulk-rock REE contents and La/Yb ratios decrease from protolithionite granite to Li-mica granite to topaz–lepidolite granite, suggesting the dominant plagioclase fractionation. This variation, together with increasing Li, Rb, Cs and Ta but decreasing Nb/Ta and Zr/Hf ratios, is consistent with the magmatic evolution. In the Yashan pluton, micas are protolithionite, muscovite, Li-mica and lepidolite, and zircons show wide concentration ranges of ZrO₂, HfO₂, UO₂, ThO₂, Y₂O₃ and P₂O₅. Compositional variations of minerals, such as increasing F, Rb and Li in mica and increasing Hf, U and P in zircon are also in concert with the magmatic evolution from protolithionite granite to Li-mica granite to topaz–lepidolite granite. The most evolved topaz–lepidolite granite has the highest bulk-rock Li, Rb, Cs, F and P contents, consistent with the highest contents of these elements and the lowest Nb/Ta ratio in mica and the lowest Zr/Hf ratio in zircon. Ta–Nb enrichment was closely related to the enrichment of volatile elements (i.e. Li, F and P) in the melt during magmatic evolution, which raised the proportion of non-bridging oxygens (NBOs) in the melt. The rims of zoned micas in the Li-mica and topaz–lepidolite granites contain lower Rb, Cs, Nb and Ta and much lower F and W than the cores and/or mantles, indicating an exotic aqueous fluid during hydrothermal evolution. Some columbite-group minerals may have formed from exotic aqueous fluids which were originally depleted in F, Rb, Cs, Nb, Ta and W, but such fluids were not responsible for Ta–Nb enrichment in the Yashan granite. The interaction of hydrothermal fluids with previously existing micas may have played an important role in leaching, concentrating and transporting W, Fe and Ti. Ta–Nb enrichment was associated with highly evolved magmas, but W mineralization is closely related to hydrothermal fluid. Thus these magmatic and hydrothermal processes explain the diversity of W and Ta–Nb mineralizations in the rare-metal granites.     

Geochemistry of magmatic and hydrothermal zircon from the highly evolved Baerzhe alkaline granite: implications for Zr–REE–Nb mineralization

The Baerzhe alkaline granite pluton hosts one of the largest rare metal (Zr, rare earth elements, and Nb) deposits in Asia. It contains a geological resource of about 100 Mt at 1.84 % ZrO₂, 0.30 % Ce₂O₃, and 0.26 % Nb₂O₅. Zirconium, rare earth elements (REE), and Nb are primarily hosted by zircon, yttroceberysite, fergusonite, ferrocolumbite, and pyrochlore. Three types of zircon can be identified in the deposit: magmatic, metamict, and hydrothermal. Primary magmatic zircon grains occur in the barren hypersolvus granite and are commonly prismatic, with oscillatory zones and abundant melt and mineral inclusions. The occurrence of aegirine and fluorite in the recrystallized melt inclusions hosted in the magmatic zircon indicates that the parental magma of the Baerzhe pluton is alkali- and F-rich. Metamict zircon grains occur in the mineralized subsolvus granite and are commonly prismatic and murky with cracks, pores, and mineral inclusions. They commonly show dissolution textures, indicating a magmatic origin with later metamictization due to deuteric hydrothermal alteration. Hydrothermal zircon grains occur in mineralized subsolvus granite and are dipyramidal with quartz inclusions, with murky CL images. They have 608 to 2,502 ppm light REE and 787 to 2,521 ppm Nb, much higher than magmatic zircon. The texture and composition of the three types of zircon indicate that they experienced remobilization and recrystallization during the transition from a magmatic to a hydrothermal system. Large amounts of Zr, REE, and Nb were enriched and precipitated during the transitional period to form the giant low-grade Baerzhe Zr–REE–Nb deposit.     

REE Minerals in the Rocks of the Katugin Rare Metal Deposit,East Transbaikalia: Behavior of Lanthanides and Y during Crystallization of an F-Saturated Agpaitic Melt

The chemical composition and origin of major REE minerals of aegirine, aegirine–arfvedsonite, arfvedsonite, and annite–riebeckite–arfvedsonite granites are studied for the Katugin Ta–Nb–Zr–Y deposit with cryolite in the southwestern part of the Aldan Shield. The REE mineralization of granites includes two types: (i) disseminated grains of pyrochlore and, to a lesser extent, other Nb–Ln oxides, Ln phosphates, and Ln–F carbonates in association with zircon, ilmenite, sphalerite, and other minerals and (ii) interstitial intergrowths of Ln fluorides.

     

Formation Process of Zircon Associated with REE‐Fluorocarbonate and Niobium Minerals in the Nechalacho REE Deposit,Thor Lake,Canada

The two drill holes, which penetrated sub‐horizontal rare earth element (REE) ore units at the Nechalacho REE in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify the enrichment mechanism of the high‐field‐strength elements (HFSE: Zr, Nb and REE). The REE ore units occur in the albitized and potassic altered miaskitic syenite. Zircon is the most common REE mineral in the REE ore units, and is divided into five types as follows: Type‐1 zircon occurs as discrete grains in phlogopite, and has a chemical character similar to igneous zircon. Type‐2 zircon consists of a porous HREE‐rich core and LREE–Nb–F‐rich rim. Enrichment of F in the rim of type‐2 zircon suggests that F was related to the enrichment of HFSE. The core of type‐2 zircon is regarded to be magmatic and the rim to be hydrothermal in origin. Type‐3 zircon is characterized by euhedral to anhedral crystals, which occur in a complex intergrowth with REE fluorocarbonates. Type‐3 zircon has high REE, Nb and F contents. Type‐4 zircon consists of porous‐core and ‐rim, but their chemical compositions are similar to each other. This zircon is a subhedral crystal rimmed by fergusonite. Type‐5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircon grains are filled by fergusonite. Type‐4 and type‐5 zircon grains have low REE, Nb and F contents. Type‐1 zircon is only included in one unit, which is less hydrothermally altered and mineralized. Type‐2 and type‐3 zircon grains mainly occur in the shallow units, while those of type‐4 and type‐5 are found in the deep units. The deep units have high HFSE contents and strongly altered mineral textures (type‐4 and type‐5) compared to the shallow units. Occurrences of these five types of zircon are different according to the depth and degree of the hydrothermal alteration by solutions rich in F and CO₃, which permit a model for the evolution of the zircon crystallization in the Nechalacho REE deposit as follows: (i) type‐1 (discrete magmatic zircon) is formed in miaskitic syenite. (ii) LREE–Nb–F‐rich hydrothermal zircon formed around HREE‐rich magmatic zircon (type‐2). (iii) type‐3 zircon crystallized through the F and CO₃‐rich hydrothermal alteration of type‐2 zircon which formed the complex intergrowth with REE fluorocarbonates; (iv) the CO₃‐rich hydrothermal fluid corroded type‐3, forming REE–Nb‐poor zircon (type‐4). Niobium and REE were no longer stable in the zircon structure and crystallized as fergusonite around the REE–Nb‐leached zircon (type‐4); (v) type‐5 zircon is formed by the more CO₃‐rich hydrothermal alteration of type‐4 zircon, suggested by the fact that type‐4 and type‐5 zircon grains are often included in ankerite. Type‐3 to type‐5 zircon grains at the Nechalacho REE deposit were continuously formed by leaching and/or dissolution of type‐2 zircon in the presence of F‐ and/or CO₃‐rich hydrothermal fluid. These mineral associations indicate that three representative hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (i) F‐rich hydrothermal stage caused the crystallization of REE–Nb‐rich zircon (type‐2 rim and type‐3), with abundant formation of phlogopite and fluorite; (ii) F‐ and CO₃‐rich hydrothermal stage led to the replacement of a part of REE–Nb–F‐rich zircon by REE fluorocarbonate; and (iii) CO₃‐rich hydrothermal stage resulted in crystallization of the REE–Nb–F‐poor zircon and fergusonite, with ankerite. REE and Nb in hydrothermal fluid at the Nechalacho REE deposit were finally concentrated into fergusonite by way of REE–Nb–F‐rich zircon in the hydrothermally altered units.     

Trace element geochemistry of scheelite and rutile from metaturbidite-hosted quartz vein gold deposits, Meguma Terrane, Nova Scotia, Canada: genetic implications

Scheelite and rutile from several metaturbidite-hosted gold-bearing quartz vein deposits of the Meguma Terrane of Nova Scotia were analyzed for trace elements including rare earth elements, niobium and tantalum. Scheelites have high concentrations of Sr, Nb, Y and rare earth elements (REE) with bell-shaped chondrite-normalized REE patterns accompanied by both positive and negative Eu anomalies. They also have high Nb/Ta ratios (80–300). Three distinct trace element types of the scheelites are interpreted to reflect chemical differences in the pulses of hydrothermal fluids. Hydrothermal rutiles have high contents of W (up to 4.2 wt.% WO₃), are rich in Ta compared to Nb and have a very low Nb/Ta ratio (~0.3). Hydrothermal fluids which produced both scheelite with a high Nb/Ta and rutile with a low Nb/Ta ratio are an efficient medium for fractionation of this ratio although these two minerals play an important role during the process.     

Ore geochemistry,zircon mineralogy,and genesis of the Sakharjok Y-Zr deposit,Kola Peninsula,Russia

The Sakharjok Y-Zr deposit in Kola Peninsula is related to the fissure alkaline intrusion of the same name. The intrusion ∼7 km in extent and 4–5 km² in area of its exposed part is composed of Neoarchean (2.68–2.61 Ma) alkali and nepheline syenites, which cut through the Archean alkali granite and gneissic granodiorite. Mineralization is localized in the nepheline syenite body as linear zones 200–1350 m in extent and 3–30 m in thickness, which strike conformably to primary magmatic banding and trachytoid texture of nepheline syenite. The ore is similar to the host rocks in petrography and chemistry and only differs from them in enrichment in zircon, britholite-(Y), and pyrochlore. Judging from geochemical attributes (high HSFE and some incompatible element contents (1000–5000 ppm Zr, 200–600 ppm Nb, 100–500 ppm Y, 0.1–0.3 wt % REE, 400–900 ppm Rb), REE pattern, Th/U, Y/Nb, and Yb/Ta ratios), nepheline syenite was derived from an enriched mantle source similar to that of contemporary OIB and was formed as an evolved product of long-term fractional crystallization of primary alkali basaltic melt. The ore concentrations are caused by unique composition of nepheline syenite magma (high Zr, Y, REE, Nb contents), which underwent subsequent intrachamber fractionation. Mineralogical features of zircon-the main ore mineral—demonstrate its long multistage crystallization. The inner zones of prismatic crystals with high ZrO₂/HfO₂ ratio (90, on average) grew during early magmatic stage at a temperature of 900–850°C. The inner zones of dipyramidal crystals with average ZrO₂/HfO₂ = 63 formed during late magmatic stage at a temperature of ∼500°C. The zircon pertaining to the postmagmatic hydrothermal stage is distinguished by the lowest ZrO₂/HfO₂ ratio (29, on average), porous fabric, abundant inclusions, and crystallization temperature below 500°C. The progressive decrease in ZrO₂/HfO₂ ratio was caused by evolution of melt and postmagmatic solution. The metamorphic zircon rims relics of earlier crystals and occurs as individual rhythmically zoned grains with an averaged ZrO₂/HfO₂ ratio (45, on average) similar to that of the bulk ore composition. The metamorphic zircon is depleted in uranium in comparison with magmatic zircon, owing to selective removal of U by aqueous metamorphic solutions. Zircon from the Sakharjok deposit is characterized by low concentrations of detrimental impurities, in particular, contains only 10–90 ppm U and 10–80 ppm Th, and thus can be used in various fields of application.     

Zircon U-Pb Geochronology and Geochemical Characteristics of the Volcanic Host Rocks from the Tongyu VHMS Copper Deposit in the Western North Qinling Orogen and Their Geological Significance

Precise in situ zircon U-Pb dating and Lu–Hf isotopic measurement using an LA-ICP-MS system, whole-rock major and trace element geochemistry and Sr–Nd isotope geochemistry were conducted on the volcanic host rocks of the Tongyu copper deposit on the basis of further understanding of its geological characteristics. Three zircon samples from the volcanic host rocks yielded 206Pb/238 U weighted average ages ranging from 436±4 Ma to 440±5 Ma, which are statistically indistinguishable and coeval with the ca. 440 Ma northward subduction event of the Paleo-Qinling oceanic slab. The volcanic host rocks were products of magmatic differentiation that evolved from basalt to andesite to dacite to rhyolite, forming an integrated tholeiitic island arc volcanic rock suite. The primitive mantle-normalized trace element patterns for most samples show characteristics of island arc volcanic rocks, such as relative enrichment of LILE(e.g. Th, U, Pb and La) and depletion of HFSE(e.g. Nb, Ta, Ti, Zr and Hf). Discrimination diagrams of Ta/Yb vs Th/Yb, Ta vs Th, Yb vs Th/Ta, Ta/Hf vs Th/Hf, Hf/3 vs Th vs Nb/16, La vs La/Nb and Nb vs Nb/Th all suggest that both the volcanic host rocks from the Tongyu copper deposit and the volcanic rocks from the regional Xieyuguan Group were formed in an island arc environment related to subduction of an oceanic slab. Values of ISr(0.703457 to 0.708218) and εNd(t)(-2 to 5.8) indicate that the source materials of volcanic rocks from the Tongyu copper deposit and the Xieyuguan Group originated from the metasomatised mantle wedge with possible crustal material assimilation. Most of the volcanic rock samples show good agreement with the values of typical island arc volcanic rocks in the ISr-εNd(t) diagram. The involvement of crustal-derived material in the magma of the volcanic rocks from the Tongyu copper deposit was also reflected in the zircon εHf(t) values, which range from-3.08 to 10.7, and the existence of inherited ancient xenocrystic zircon cores(2616±39 Ma and 1297±22 Ma). The mineralization of the Tongyu copper deposit shows syn-volcanic characteristics such as layered orebodies interbedded with the volcanic rock strata, thus, the zircon U-Pb age of the volcanic host rocks can approximately represent the mineralization age of the Tongyu copper deposit. Both the Meigou pluton and the volcanic host rocks were formed during the ca. 440 Ma northward subduction of the Paleo-Qinling Ocean when high oxygen fugacity aqueous hydrothermal fluid released by dehydration of the slab and the overlying sediments fluxed into the mantle wedge, triggered partial melting of the mantle wedge, and activated and extracted Cu and other ore-forming elements. The magma and ore-bearing fluid upwelled and erupted, and consequently formed the island arc volcanic rock suite and the Tongyu VHMS-type copper deposit.     

Trace-element study and age dating of zircon from chromitites of the Bushveld Complex (South Africa)

The layered Bushveld Complex hosts a number of chromitite layers, which were found to contain significant amounts of zircon grains compared with adjacent silicate rocks. Cathodoluminescent-dark, partially metamict cores and transparent rims of composite zircon grains were analyzed for trace elements with SIMS and LA-ICPMS techniques. The cores are enriched in REE, Y, Th and U and are characterized by distinctly flatter REE patterns in contrast to those of the rims and transparent homogenous crystals. Zircon from the different stratigraphic units has specific Th/U ratios, the highest of which (1.5–4) occurs in a Merensky Reef zircon core. The Ti content of Bushveld zircon ranges from 12 to 52 ppm correlating to a crystallization temperature range of 760–930 °C. The geochemical characteristics of the first zircon generation are consistent with its high-temperature crystallization as the first major U, Th and REE acceptor from a highly-evolved residue of the high-Mg basalt magma, whereas the rims and coreless crystals have crystallized from percolating intercumulus liquid of new influx of the same magma. U-Pb SHRIMP dating of zircon cores and rims does not reveal a distinguishable difference between their ages indicating the absence of inherited zircon. Concordia ages of 2,051?±?9 Ma (2σ, MSWD?=?0.1) and 2,056?±?5 Ma (2σ, MSWD?=?0.05) for zircons from the Merensky Reef and the Upper Platreef located equally near the top of the Critical Zone are in agreement with published ages for the Merensky Reef. Zircon from the deeper-seated Lower Group, Middle Group and Lower Platreef chromitites yields younger concordia ages that may reflect prolonged late-stage volatile activity.     

Determination of the Neoproterozoic Shicaogou Syn-collisional Granite in the Eastern Qinling Mountains and Its Geological Implications

The Shicaogou granite has been identified as a magnesian (Fe-number=0.71-0.76), calcic to calc-alkalic (MALI=3.84-5.76) and peraluminous (ASI=1.06-1.13) granite of the syn-collisional S-type, with high SiO2(>71%), A12O3 (>13%) and Na2O+K2O (6.28%-7.33%, equal for NaO2 and K2O). Trace element and REE analyses show that the granite is rich in LILE such as of Rb, Sr, Ba and Th, and poor in HFSE like Yb, Y, Zr and Hf. Its Rb/Sr ratio is greater than 1; the contents of Nb and Ta, and the ratio of Nb/Ta as well as the REE geochemical features (e.g. REE abundance, visible fractionation of LREE and HREE and medium to pronounced negative Eu anomalies) are all similar to those of crust-origin, continent-continent syn-collisional granite. Moreover, the granite exhibits almost the same pattern as that of the typical continent-continent syn-collisional granite on the spider diagram and all samples fall within the syn-collisional granite field.The cathodoluminescence (CL) investigations have revealed that the zircon f     

大别山高压?超高压片麻岩核?边结构锆石成因探讨*

大别山高压?超高压片麻岩中的锆石在阴极发光(CL)显示核?边结构：韵律环带的岩浆锆石核,较强发光的变质边。本文对核?边结构的锆石进行了包裹体、微区U?Pb年龄和微量元素研究。结果表明变质边由两种不同的机制形成：变质重结晶和变质增生。变质重结晶锆石的U?Pb年龄和稀土总量逐渐降低,稀土配分模式不变。变质增生锆石比变质重结晶锆石具有更低Th/U比值,重稀土严重亏损,Eu负异常不明显,低的Nb、Ta含量。     

Chemistry of Zircon in Rare Metal Granitoids and Associated Rocks, Eastern Desert, Egypt

Typological study, including paragenic, morphological, textural, and chemical characteristics of zircon from nine rare metal granitic stocks and associated greisens, was carried out in order to identify the metallogenic processes of their host granitoids. The investigated zircon‐bearing granitoids and type occurrences can be categorized into magmatically and metasomatically specialized types. The magmatic type includes: (i) peralkaline, Zr + Nb‐enriched, A₁‐granite (e.g. Um Hibal); (ii) metaluminous, Nb + Zr + Y‐enriched, A₂‐type alkali granite (e.g. Hawashia and Ineigi); and (iii) peraluminous, Ta ≥ Nb + Sn + Be ± W‐enriched, Li‐albite granite (e.g. Nuweibi, Igla and Abu Dabbab). The metasomatized granites are Nb>>Ta + Sn + Zr + Y + U ± Be ± W‐enriched and hydrothermally altered alkali feldspar granite (i.e. apogranite; e.g. Um Ara, Abu Rusheid, and Um Naggat). Zircon of peralkaline granite is characteristically equant with well‐developed pyramidal faces and short prisms (i.e. pseudo‐octahedral form) with length/width ratios in the range of 2:1–1:1. It is of Zr_0.990Hf_0.007SiO₄ composition and is associated with hypersolvus assemblage consisting of alkali feldspar, quartz, aegirine and minor reibeckite. Zircon of metaluminous alkali granites is of Zr_0.99Hf_0.01SiO₄ composition and is associated with sub‐ to transolvus assemblage of K‐feldspar, quartz, plagioclase and annite‐siderophyllite mica. It is prismatic with length/width ratios in the range of 5:1–3:1, doubly terminated with small pyramidal faces. Compositionally, zircon of Li‐albite granite ranges between Zr_0.925Hf_0.075SiO₄ and Zr_0.705Hf_0.295SiO₄. It is idiomorphic with a simple combination of prism and bipyramidal terminations with a length/width ratio of 3:1–2:1. This zircon commonly exhibits a normal zoning with rims consistently higher in Hf than cores. The higher Hf content, of this zircon coupled with its association with topaz, tantalite and lithian micas (e.g. zinnwaldite and Li‐white mica), indicates a higher solubility of Hf‐fluoride complexes and their more stabilized state at lower temperature in Li‐ and F‐rich sodic melts. Zircon of apogranite association ranges in composition between Zr_0.967Hf_0.013SiO₄ in the lower unaltered alkali feldspar granite zone and Zr_0.805Hf_0.064(Y, U, Th, heavy rare‐earth elements) [HREE])_0.125SiO₄ in the apical metasomatized (i.e. microclinized, albitized, and greisenized) apogranite zones. This compositional change appears to reflect a roofward increasing in μ_KF, μ_NaF, and μ_HF of the exsolved fluids. Columbite, xenotime, thorite, cassiterite, beryl and fluorite are common associates of this zircon. This zircon is of bipyramidal to typical octahedral form with complete absence of prism concurrently with conspicuous development of pyramid, thus the zircon crystals have a length/width ratio of 1:1–0.5:1. The neoformed metasomatic zircon commonly exhibits either normal or reverse zoning with rims consistently different in Hf, U, Y, and HREE than cores, reflecting disequilibrium conditions (e.g. sudden change in P, T, salinity, and pH) between the growing crystals and the exsolved fluids.     

Trace element distribution in mineral inclusions in zoned garnets from eclogites of the Atbashi Range (South Tianshan)

Ion microprobe data for minerals from the eclogites of the Atbashi Range (South Tianshan) constrain the distribution of trace (Rb, Sr, Ba, Cr, V, Zr, Hf, Nb, Ta, U, Th, and Y) and rare-earth elements (REE) in zoned garnets and mineral inclusions in them. This study showed that garnets from the Atbashi eclogites are the main hosts for heavy REE; epidotes are important hosts for REE, Y, Sr, Th, and U; and omphacites are depleted in almost all trace elements compared with the bulk-rock compositions. Garnet, as well as epidote and omphacite inclusions exhibit systematic rimward depletion in a number of trace elements, which is related to the depletion of the rock matrix in these elements during crystallization. Deviations from this trend, including the enrichment of garnet rims in HREE and strong variations in the REE contents of garnets and mineral inclusions, can be explained by metamorphic reactions involving the destabilization of REE-bearing minerals. Our data suggest that the mobility of trace elements under eclogites-facies conditions is mainly controlled by the stability of certain minerals.     

Compositional characteristics of wolframite in tin deposits,Dupangling, Guangxi

Statistical data on major, trace and rare-earth elements in wolframite from the quartz vein-and greisen-type tin deposits in the Dupangling orefield reveal: (1) The components in wolframite can be divided into two relatively independent groups: the WO₃-Nb-Ta-Sc-REE group, in which WO₃ is negatively correlated with the others and the FeO-MnO-Sn group, in which MnO is negatively correlated with the other two; (2) In general, REE fractionation is not significant, reflected mainly by the separation of Eu from other REE’s. LREE and HREE increase or decrease simultaneously, with HREE being more variable; (3) Nb, Ta, Sc, REE substitute for W, and Sn may enter into wolframite lattice accompanied by Fe-Mn substitution; (4) In contrast to wolframite in quartz veins, which is poor in REE, Nb, Ta and Sc and has highδ Eu values and LREE / HREE and Nb/Ta ratios, wolframite in greisen is rich in REE, Nb, Ta, Sc and has lowδ Eu values and LREE/HREE and Nb/Ta ratios; and (5) The contents and ratios of trace elements and REE partitioning parameters of wolframite can be used as guide for prospecting.     

Hydrothermal alteration and evolution of Zr-Th-U-REE mineralization in the microgranite of Wadi Ras Abda,North Eastern Desert,Egypt

Ras Abda plutonic suite, North Eastern Desert of Egypt, consists predominantly of Neoproterozoic calc-alkaline older granites. Minor exposures of pink microgranite are occurring along Wadi Ras Abda within the older granites. Previous studies on this area demonstrated that the microgranite is altered in some parts and contains anomalous concentrations of rare metal elements (Zr, Th, and U). These altered and mineralized zones are re-assessed using field observations, chemical analysis, and by the application of various transmitted light and electron microscopic techniques. The rare metals exist as mineral segregation grew freely into open cavities of the microgranite and concordant with the NNE strike-slip fault movement. The mineralized zones contain an assemblage of secondary magnetite, zircon, uranothorite, columbite-(Mn), fergusonite-(Y), and allanite-(Ce). The extreme abundance of zircon in the mineralized zone, along with other evidence, indicates a hydrothermal origin of this zircon together with associated rare metals. The geochemical investigation and mass balance calculations revealed extreme enrichment of Zr, Th, U, Y, Nb, Ta, and REE. Post-magmatic hydrothermal alterations resulted in such pronounced chemical and mineralogical heterogeneity. The hydrothermal fluids are thought to be oxidizing, alkaline and of medium temperature (>?250 °C). The average contents of the elements Zr (1606 ppm), Th (1639 ppm), U (306 ppm), Nb (955 ppm), and REE (1710 ppm) in the mineralized microgranite reach sub-economic levels and could be a potential source of these elements.     

Trace and rare earth elements as indicators of provenance and depositional environments of Lias cherts in Gumushane,NE Turkey

Trace elements and rare earth elements (REEs) of Lias-aged cherts in the Gumushane area were studied in order to understand their origin and depositional environment. Twenty three chert samples from five stratigraphic sections were analysed by inductively coupled plasma-mass spectrometry, X-ray diffraction, and mineralogical investigation. Lias cherts in the study area are microcrystalline, cryptocrystalline quartz, and megaquartz depending on mineralogical content. Trace elements of the cherts were compared with PAAS, Co, Y, and Th had stronger depletions in the five sections, whereas V, Ni, Zr, Nb, and Hf had smaller depletions. The distribution of Zr, Hf, and Ta yields Zr/Hf, Zr/Ta and Hf/Ta ratios (25/645, 37/665, and 0.18/3, respectively) that differ from those of chondrites and average upper continental crust, suggesting that these elements are likely non-detrital but are sourced from seawater. Th/U ratios range from 0.04 to 0.45 and are lower than those of the upper continental crust (average: 3.9). Lias-aged cherts have low total REE abundances and stronger depletions in five sections of the PAAS and chondrite-normalised plots. The cherts are characterised by a positive Eu anomaly (average: 4.9) and LREE-enrichment (La_N/Yb_N = average: 3.5). In addition, about one-half of the cherts exhibit positive Ce anomaly (range: 0.25–2.58), chondritic Y/Ho values (range: 3.3–60), and low (La/Ce)_N values (average: 1.8). REE and trace element abundance in Lias cherts indicate that these elements were likely derived from hydrothermal solutions, terrigenous sources, and seawater. The REE patterns of the cherts show that they were probably deposited close to a continental margin.     

Amphibole and phlogopite in “hybrid” metasomatic bands monitor trace element transfer at the interface between felsic and ultramafic rocks (Eastern Alps,Italy)

Ultramafic rocks in contact to gneisses in the Mt. Hochwart HP mélange (Eastern Italian Alps) preserve a series of metasomatic mineral zones. A phlogopitite with minor tremolite and accessory zircon and apatite forms close to the gneiss (Zone 1). Zone 2 consists of tremolite, phlogopite and anthophyllite followed by Zone 3 with anthophyllite plus minor chlorite and talc. Zone 3 grades into an amphibole–garnet peridotite lens. This reaction zone has been generated by infiltration of hydrous fluids at T of 660–700 °C and P < 1.2 GPa, which occurred during exhumation of coupled continental crust and mantle peridotites.The reaction zone between a trace element-rich (gneiss) and a trace element depleted reservoir (peridotite) allows assessment of local trace element mobility in aqueous fluids. We present the results of in situ LA-ICP-MS trace element analysis of minerals from the reaction zone. Phlogopite is the main host for Large Ion Lithophile Elements (LILE) and contributes significantly to the Li, Ti, Nb, Ta, Pb and Sc budget. Anthophyllite is the main host for Li whereas all other trace elements including Rare Earth Elements (REE) are preferentially incorporated into tremolite. Combined with the abundance of these minerals over the contact zone, the mineral trace element data suggests that the LILE and REE were mobile on a small scale of a few centimetres only. Limited mobility of Ta, which is generally regarded as barely mobile in fluids, is documented in elevated contents of Ta in anthophyllite coupled with low Nb/Ta. The high Li content in minerals throughout the reaction zone suggests that Li was the most mobile element.The studied metasomatic zones mirror geochemical processes occurring in subduction zones at the slab–mantle interface. Phlogopite crystallization at the slab–mantle interface is an efficient mechanism to filter LILE from the aqueous fluid. Thus, such reaction zones, forming at temperatures < 660–700 °C, likely prevents that the typical slab signature with enriched LILE is transported by aqueous fluids over long distances in the mantle wedge. However, if coupled to the downgoing slab, phlogopite- and tremolite-rich rocks from such reaction zones might be able to act as carriers of trace elements and water into deeper parts of the subduction zone.