Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

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.     

Morphology and impurity elements of zircon in the oceanic lithosphere at the Mid-Atlantic ridge axial zone (6°–13° N): Evidence of specifics of magmatic crystallization and postmagmatic transformations

The paper presents newly obtained original data on the morphology, internal structure (as seen in cathodoluminescence images, CL), and composition of more than 400 zircon grains separated from gabbroids and plagiogranites (OPG) sampled at the axial zone of the Mid-Atlantic Ridge (MAR). The zircons were analyzed for REE by LA-ICP-MS and for Hf, U, Th, Y, and P by EPMA. Magmatic zircon in the gabbroids crystallized from differentiating magmatic melt in a number of episodes, as follows from systematic rimward increase in the Hf concentration, and also often from the simultaneous increase in the (U + Th) and (Y + P) concentrations. These tendencies are also discernible (although much less clearly) in zircons from the OPG. Zircon in the OPG is depleted in REE compared to the least modified zircons in the gabbro, which suggests that the OPG were derived via partial melting of gabbro in the presence of seawater-derived concentrated aqueous salt fluid. Another reason for the REE depletion might be simultaneous crystallization of zircon and apatite. The CL-dark sectors, which are found in practically all of the magmatic zircon grains, have Y/P (a.p.f.u.) ? 1 which most likely resulted from OH accommodation in the zircon structure, a fact suggesting that the OPG parental melt contained water. High-temperature hydrothermal processes induced partial to complete recrystallization of zircon (via dissolution-reprecepitation), a process that was associated with ductile and brittle deformations of the zircon-hosting rocks. The morphology of the hydrothermal zircons varies depending on pH and silica activity in the fluid from weakly corroded subhedral crystals with typical vermicular microtopography of the crystal faces to completely modified grains of colloform structure. Geochemically, the earlier hydrothermal transformations of the zircons resulted in their enrichment in La and other LREE, except only Ce, whose concentration, conversely, decreases compared to that of the unmodified magmatic zircons. The hydrothermal zircon displays a reduced Ce anomaly and its most altered domains typically host minute inclusions of xenotime, U and Th oxides and silicates, and occasionally also baddeleyite, which suggests that the hydrothermal fluid was reduced and highly alkaline. These features were acquired by the seawater-derived fluid when it circulated within the axial MAR zone area due to phase separation in the H₂O–NaCl system and particularly as a result of fluid interaction with the abyssal peridotites of oceanic core complexes. Our data demonstrate that zircon is a sensitive indicator of tectonic and physicochemical processes in the oceanic crust.     

Host rock compositional controls on zircon trace element signatures in metabasites from the Austroalpine basement

Zircon populations of Neoproterozoic and early Paleozoic age occur in metabasites of a high-pressure amphibolite-facies unit of the Austroalpine basement south of the Tauern Window. The host rocks for these zircons are eclogitic amphibolites of N-MORB-type character, hornblende gneisses with volcanic-arc basalt signature, and alkaline within-plate-basalt amphibolites. Bulk rock magmatic trace element patterns were preserved during amphibolite-facies high-pressure and subsequent high-temperature events, as well as a greenschist-facies overprint. Positive Ce and negative Eu anomalies and enrichment of HREE in normalized zircon REE patterns, as analysed by LA-ICP-MS, are typical for an igneous origin of these zircon suites. Zircon Y is well correlated to HREE, Ce, Th, U, Nb, and Ta and allows discrimination of compositional fields for each host rock type. Low Th/U ratios are correlated to low Y and HREE abundances in zircon from low bulk Th/U host rocks. This is likely a primary igneous characteristic that cannot be attributed to metamorphic recrystallization. Variations of zircon/host rock element ratios confirm that ionic radii and charges control abundances of many trace elements in zircon. The trace element ratios—presented as mineral/melt distribution coefficients—indicate a selectively inhibited substitution of Zr and Si by HREE and Y in zircon which crystallized from a N-MORB melt. Correlated host rock and zircon trace element concentrations indicate that the metabasite zircons are not xenocrysts but crystallized from mafic melts, represented by the actual host rocks.     

Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

Ion-microprobe zircon geochemistry as an indicator of mineral genesis during geochronological studies

This paper considers the distribution of trace elements (including rare earth elements) in zircons dated by the ion-microprobe U-Th-Pb isotope method and its genetic implications. Two problems were addressed on the basis of the investigation of trace element compositions of zircons: (1) genesis of zircons from subalkaline magmatic rocks, sysenites, and sanukitoids and their comparison with tonalites as exemplified by the rocks of the Karelian region, and (2) determination of trace element signatures of zircons from the oldest granulite-facies rocks of the Ukrainian shield. It was shown that the REE distribution patterns of the tonalites, which crystallized in equilibrium with melt, are strictly governed by crystal-chemical laws. The REE distribution patterns show a positive slope with an increase from La to Lu, a positive Ce anomaly, and a negative Eu anomaly. Similar patterns were observed in zircons from the syenites. The trace element contents of zircons are related to those of melts through partition coefficients. Zircons from the sanukitoids show a considerable LREE enrichment, which is inconsistent with the calculated zircon/melt partition coefficients and presumably related to the inherently imperfect zircon structure. Such a structure was formed during zircon crystallization from melt at high temperatures and the anomalous fluid regime that is characteristic, in particular, of sanukitoid melts. The REE distribution patterns of zircons that crystallized under granulite-facies conditions are sharply different from typical distributions in HREE depletion, which was caused by the competitive growth of garnet during zircon crystallization.     

The influence of fractionation of REE-enriched minerals on the zircon partition coefficients

Zircon is widely used to simulate melt generation, migration and evolution within the crust and mantle.The achievable performance of melt modelling generally depends on the availability of reliable trace element partition coefficients(D).However, a large range of D_(REE)values for zircon from natural samples and experimental studies has been reported, with values spanning up to 3 orders of magnitude.Unfortunately, a gap of knowledge on this variability is evident.In this study we model the crystallization processes of common REE-bearing minerals from granitic melts and show that the measured zircon D_(REE)would be elevated if there is crystallization of REE-enriched minerals subsequent to zircon.Nevertheless, compared to zircon D_(REE)values measured from experimental studies, this mechanism appears to have a less significant influence on those from natural granite samples since the quantity of crystallized REE-enriched minerals is very low in natural magmatic systems and/or most of them crystallize prior to zircon.Combined with recently published studies, this work supports that analysis of natural zircon/host groundmass pairs provides more robust D_(REE)values applicable to natural systems than those measured from experimental studies, which can be used to constrain the provenance of detrital zircons.     

Trace elements in various genetic types of zircon from syenite of the Sakharjok massif,Kola Peninsula

Zircon is an accessory mineral in alkali and nepheline syenites of the Neoarchean Sakharjok intrusion. Zircon in association with britholite and pyrochlore forms orebodies in nepheline syenite of this massif. Zircon crystals reveal an inhomogeneous zonal, occasionally mosaic structure comprising fragments and zones related to magmatic, hydrothermal, and metamorphic stages of mineral formation. Magmatic zircon differs by a high REE concentration (1769 ppm, on average), distinct Ce maximum (Ce/Ce* = 105, on average), and Eu minimum (Eu/Eu* = 0.19) as compared with other genetic types. No correlation between these parameters has been established. Hydrothermal zircon is characterized by a low Ce/Ce* ratio (0.7–3.9 and 2.0, on average), elevated LREE contents, and lowered ratios of MREE and HREE to La. Metamorphic zircon differs from magmatic by a sharply lower REE concentration (385 ppm, on average), lowered Th/U (0.32) and Ce/Ce* (31.9, on average) ratios. In the Ce/Ce* versus MREE/La plot, the lowest values of these ratios are typical of hydrothermal zircon, while the intermediate and maximum values are inherent to metamorphic and magmatic zircons, respectively. These variations make it possible to delineate reliable fields of their compositions. The distribution of data points in the above-mentioned plots shows that REE chemical activity depends on the redox conditions of zircon crystallization.     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills,Australia

Hydrothermal zircon can be used to date fluid-infiltration events and water/rock interaction. At the Boggy Plain zoned pluton (BPZP), eastern Australia, hydrothermal zircon occurs with hydrothermal scheelite, molybdenite, thorite and rutile in incipiently altered aplite and monzogranite. The hydrothermal zircon is texturally distinct from magmatic zircon in the same rocks, occurring as murky-brown translucent 20–50 μm-thick mantles on magmatic cores and less commonly as individual crystals. The hydrothermal mantles are internally textureless in back-scatter electron and cathodoluminescence images whereas magmatic zircon is oscillatory zoned. The age of the hydrothermal zircon is indistinguishable from magmatic zircon, indicating precipitation from a fluid evolved from the magma during the final stages of crystallization. Despite indistinguishable U-Pb isotopic compositions, the trace-element compositions of the hydrothermal and magmatic zircon are distinct. Hydrothermal zircon is enriched in all measured trace-elements relative to magmatic zircon in the same rock, including V, Ti, Nb, Hf, Sc, Mn, U, Y, Th and the rare-earth elements (REE). Chondrite-normalized REE abundances form two distinct pattern groupings: type-1 (magmatic) patterns increase steeply from La to Lu and have Ce and Eu anomalies—these are patterns typical for unaltered magmatic zircon in continental crust rock types; type-2 (hydrothermal) patterns generally have higher abundances of the REE, flatter light-REE patterns [(Sm/La)_N = 1.5–4.4 vs. 22–110 for magmatic zircon] and smaller Ce anomalies (Ce/Ce* = 1.8–3.5 vs. 32–49 for magmatic zircon). Type-2 patterns have also been described for hydrothermally-altered zircon from the Gabel Hamradom granite, Egypt, and a granitic dyke from the Acasta Gneiss Complex, Canada.Hadean (∼4.5–4.0 Ga) zircon from the Jack Hills, Western Australia, have variable normalized REE patterns. In particular, the oldest piece of Earth—zircon crystal W74/2-36 (dated at 4.4 Ga)—contains both type-1 and type-2 patterns on a 50 μm scale, a phenomenon not yet reported for unaltered magmatic zircon. In the context of documented magmatic and hydrothermal zircon compositions from constrained samples from the BPZP and the literature, the type-2 patterns in crystal W74/2-36 and other Jack Hills Hadean (JHH) zircon are interpreted as hydrothermally-altered magmatic compositions. An alteration scenario, constrained by isotope and trace-element data, as well as α-decay event calculations, involving fluid/zircon cation and oxygen isotope exchange within partially metamict zones and minor dissolution/reprecipitation, may have occurred episodically for some JHH zircon and at ∼4.27 Ga for zircon W74/2-36. Type-2 compositions in JHH zircon are interpreted to represent localized exchange with a light-REE-bearing, high δ¹⁸O (∼6–10‰ or higher) fluid. Thus, a complex explanation involving “permanent” liquid water oceans, large-scale water/rock interaction and plate tectonics in the very early Archean is not necessary as the zircon textures and compositions are simply explained by exchange between partially metamict zircon and a low volume ephemeral fluid.     

Trace and rare earth elements in cassiterite — sources of components for the tin deposits of the Mole Granite,Australia

Trace and rare earth elements have been determined for cassiterite from deposits associated with the Mole Granite and hosted by granite, metasediments and metavolcanics. The REE of cassiterite is controlled by the REE of the the ore fluid and the rocks through which this fluid circulated. The REE distribution factor and LREE/HREE value of cassiterite is strongly influenced by the associated mineral assemblage, the fluid chemistry and the crystal chemical characteristics of the host mineral. Cassiterite from deposits hosted by granite have trace and rare earth element characteristics similar to those determined for the Mole Granite. Cassiterite from deposits hosted by metasediments or acid volcanics have most trace and rare earth element characteristics similar to those of the enclosing rocks and some characteristics similar to the Mole Granite. The ore fluid had chemical components derived from the parental granite and components acquired by passage through the metamorphosed aureole.     

辽东半岛早白垩世早期高分异花岗伟晶岩成因与构造背景

包括辽东半岛在内的华北克拉通北缘早白垩世早期岩浆活动极其稀少,研究程度较低,导致该时期的地质背景限定缺乏直接证据.对辽东半岛三股流地区新发现的花岗伟晶岩开展了岩石学、锆石U-Pb年代学、锆石阴极发光（CL）成像技术、锆石微量元素、全岩地球化学和锆石Lu-Hf同位素等方面的研究,以期为研究区早白垩世早期构造背景提供制约.花岗伟晶岩锆石阴极发光微弱甚至不发光,大多数锆石内部结构为斑杂状分带或海绵状分带,少见岩浆震荡环带,Th/U < 0.1,其锆石稀土元素特征也与岩浆锆石明显不同,显示出热液锆石特征.锆石U-Pb年代学结果表明花岗伟晶岩的形成年龄为144.3±2.7 Ma,属早白垩世早期.花岗伟晶岩以富Si、Al、碱,贫Fe、Mg,富集大离子亲石元素,亏损高场强元素,以及显示出一定的四分组效应为特征.其ε_Hf（t）为-27.4~-24.7,二阶段模式年龄为2.91~2.74 Ga,与五龙中晚侏罗世花岗岩Hf同位素组成相类似.综合以上研究,认为三股流花岗伟晶岩经历了较高程度的分异结晶,与五龙中晚侏罗世花岗岩存在成因联系,其成岩介质为富含热液的岩浆-热液共存体系.辽东半岛早白垩世早期岩浆活动形成于伸展背景,该伸展背景可能与蒙古-鄂霍茨克洋后碰撞伸展和太平洋俯冲相关.      

不同成因锆石阴极发光及微量元素特征:以新疆阿尔泰地区花岗岩和伟晶岩为例

新疆阿勒泰可可托海地区出露大量花岗岩和伟晶岩脉,利用阴极发光显微照相(CL)、电子探针背散射(BSE)和激光剥蚀电感耦合等离子质谱技术(LA-ICP-MS),观察和分析岩石中锆石的内部结构、稀土元素及Th,U含量后结果表明:该区花岗岩锆石具振荡环带和强烈的阴极发光特征,Th/U比值较高(Th/U=0.16～0.99),轻稀土亏损、重稀土富集,具较大的Ce正异常,为典型岩浆成因锆石。伟晶岩(KP-08-11)锆石为热液锆石,不具振荡环带和阴极发光,具低的Th/U比值(0.01～0.13),强烈富集稀土元素,尤其是轻稀土元素较花岗岩锆石高一个数量级,Ce的正异常相对较低。伟晶岩(KP3-08-1)锆石为变质重结晶锆石,Th/U比值分布范围较广(0.01～0.78),强烈亏损稀土元素,稀土元素配分模式存在显著的"REE四分组效应"。微量元素特征表明,伟晶岩(KP-08-11)锆石可能结晶自富U贫Th的残余岩浆流体,而伟晶岩(KP3-08-1)的锆石经历了蜕晶质化和变质重结晶作用,但依然保持了共存伟晶岩熔体的微量元素特征。     

Ra’s Abdah of the north Eastern Desert of Egypt: the role of granitic dykes in the formation of radioactive mineralization,evidenced by zircon morphology and chemistry

Syenogranitic dykes in the north of Egypt’s Eastern Desert are of geological and economic interest because of the presence of magmatic and supergene enrichment of radioactive mineralization. Zircon crystal morphology within the syenogranitic dykes allows precise definition of sub-alkaline series granites and crystallized at mean temperature of about 637 °C. The growth pattern of the zircons suggest magmatic and hydrothermal origins of radioactive mineralization. Hydrothermal processes are responsible for the formation of significant zircon overgrowth; high U-zircon margins might have occurred contemporaneously with the emplacement of syenogranitic dykes which show anomalous uranium (eU) and thorium (eTh) contents of up to 1386 and 7330 ppm, respectively. Zircon chemistry revealed a relative increase of Hf consistent with decreasing Zr content, suggesting the replacement of Zr by Hf during hydrothermal activity. Visible uranium mineralization is present and recognized by the presence of uranophane and autunite.     

U and Th Contents and Th/U Ratios of Zircon in Felsic and Mafic Magmatic Rocks: Improved Zircon-Melt Distribution Coefficients

High-precision data on U and Th contents and Th/U ratios of zircon obtained using secondary ion mass spectrometry analysis have been collected from the literature. Zircon in the granitic rocks has median values of 350 ppm U, 140 ppm Th, and Th/U=0.52; the recommended zircon-melt partition coefficients are 81 for DU and 8.2 for DTh. In zircon from mafic and intermediate rocks, the median values are 270 ppm U, 170 ppm Th, and Th/U=0.81, and the recommended zircon-melt partition coefficients are 169 for DU and 59 for DTh. The U and Th contents and Th/U ratios of magmatic zircon are low when zircon crystallizes in equilibrium with the melt. Increasing magma temperature should promote higher Th contents relative to U contents, resulting in higher Th/U ratios for zircon in mafic to intermediate rocks than in granitic rocks. However, when zircon crystallizes in disequilibrium with the melt, U and Th are more easily able to enter the zircon lattice, and their contents and Th/U ratios depend mainly on the degree of disequilibrium. The behavior of U and Th in magmatic zircon can be used as a geochemical indicator to determine the origins and crystallization environments of magmatic zircon.     

Zircon in gabbroids from the axial zone of the Mid-Atlantic ridge, Markov Deep, 6° N: Correlation of geochemical features with petrogenetic processes

This paper reports the results of detailed petrological-geochemical study of zircons and host rocks that were dredged from the Markov Deep area in the slow-spreading Mid-Atlantic ridge. The rocks are represented by variably cataclased gabbronorite with veinlets of oceanic plagiogranite (OPG) as well as leucocratic gabbro (primitive gabbro) and hornblende Fe-Ti oxide gabbronorite (ferrogabbro) without OPG. The studied zircons differ in morphology, inner structure, set of mineral inclusions (ingrowths), and content of trace elements. Compositional heterogeneity is also observed within individual grains. The REE distribution patterns in zircons are characterized by gentle growth from LREE to HREE, with prominent positive Ce anomaly and negative Eu anomaly, and in general fall in the range of zircons from magmatic rocks. Oceanic zircons clearly differ from continental populations in the U/Yb-Y and U/Yb-Hf discrimination diagrams, primarily, due to their lower U/Yb ratio at wide variations of Y and Hf contents. Zircons that contain inclusions of acid glass and hence, crystallized from OPG melt are relatively depleted in REE, especially HREE. This indicates that OPG was formed by partial melting of gabbro in the presence of concentrated water-salt fluid, which extracted REE from the plagiogranite melt. Zircons from gabbroids devoid of OPG inclusions have higher total REE contents than zircons from OPG. Late hydrothermal alterations of zircon are distinctly established by the formation of neogenic collomorphic (porous) texture and/or by composition of mineral inclusions and accompanied by significant enrichment in La. Heterogeneous distribution of Ti in zircon may be caused not only by a change in its crystallization temperature, but also variations in silica to titanium oxide activity ratios in the rocks during interaction with hydrothermal solution of variable acidity. A complex study of structural-morphological and geochemical features of oceanic zircons and phase composition of host rocks and inclusions provides insight into processes leading to the crystallization and subsequent evolution of this mineral in the rocks of oceanic lithosphere.     

Geochemical Features of Vein Anhydrite from the Kakkonda Geothermal System, Northeast Japan

Abstract. Cathodoluminescence (CL) color, rare earth element (REE) content, sulfur and oxygen isotopes and fluid inclusions of anhydrite, which frequently filled in hydrothermal veins in the Kakkonda geothermal system, were investigated to elucidate the spatial, temporal and genetical evolution of fluids in the deep reservoir. The anhydrite samples studied are classified into four types based on CL colors and REE contents: type-N (no color), type-G (green color), type-T (tan color) and type-S (tan color with a high REE content). In the shallow reservoir, only type-N anhydrite is observed. In the deep reservoir, type-G anhydrite occurs in vertical veins whereas type-T and -N in lateral veins. Type-S anhydrite occurs in the heat-source Kakkonda Granite. The CL textures revealed that type-G anhydrite deposited earlier than type-T in the deep reservoir, implying that fracture system was changed from predominantly vertical to lateral.
Studies of fluid inclusions and δ³⁴S and δ¹⁸O values of the samples indicate that type-N anhydrite deposited from diluted fluids derived from meteoric water, whereas type-G, -T and -S anhydrites deposited from magmatic brines derived from the Kakkonda Granite with the exception of some of type-G with recrystallization texture and no primary fluid inclusion, which deposited from fossil seawater preserved in the sedimentary rocks. Type-G, -T and -S anhydrites exhibit remarkably different chondrite-normalized REE patterns with a positive Eu anomaly, with a convex shape (peak at Sm or Eu) and with a negative Eu anomaly, respectively. The difference in the patterns might result from the different extent of hydrothermal alteration of the reservoir rocks and contribution of the magmatic fluids.     

Inhomogeneous distribution of REE in scheelite and dynamics of Archaean hydrothermal systems (Mt. Charlotte and Drysdale gold deposits, Western Australia)

Scheelite is a widespread accessory mineral in hydrothermal gold deposits, and its rare earth element (REE) patterns and Nd and Sr isotopic compositions can be used to constrain the path and origin of the mineralising fluids and the age of the hydrothermal activity. Micro-analyses by laser ablation high resolution inductively coupled mass spectroscopy and cathodoluminescence imaging reveal a very inhomogeneous distribution of the REE in single scheelite grains from the Mt. Charlotte and Drysdale Archaean gold deposits in Western Australia. Two end-member REE patterns are distinguished: type I is middle REE (MREE)-enriched, with no or minor positive Eu-anomaly, whereas type II is flat or MREE-depleted with a strong positive Eu-anomaly. The chemical inhomogeneity of these scheelites is related to oscillatory zoning involving type I and type II patterns, with zone widths varying from below 1 to 200 μm. Intra-sectorial growth discontinuities, syn-crystallisation brittle deformation, and variations in the relative growth velocities of crystallographically equivalent faces suggest a complex crystallisation history under dynamic hydraulic conditions. The co-existence of MREE-enriched and MREE-depleted patterns within single scheelite crystals can be explained by the precipitation of a mineral which strongly partitions MREE relative to light and heavy REE. Scheelite itself has such characteristics, as does fluorapatite, which is locally abundant and has REE contents similar to that of scheelite. In this context, the systematic increase of the Eu-anomaly between type I and type II patterns is produced by the difference between the partition coefficients of Eu²⁺ and Eu³⁺, and not by fluid mixing or redox reactions. Consequently, the high positive Eu-anomaly typical of scheelite from gold ores may not necessarily be inherited from the hydrothermal fluid, but may reflect processes occurring during ore deposition. This case study demonstrates that in hydrothermal systems characterised by low REE concentrations in the fluid, and by the precipitation of a REE-rich mineral which strongly fractionates the REE, the REE patterns of such a mineral will be highly sensitive to the dynamics of the hydrothermal system. Received: 1 November 1999 / Accepted: 4 February 2000     

Geochronology and mineralogy of the Weishan carbonatite in Shandong province,eastern China

The Weishan REE deposit is located at the eastern part of North China Craton (NCC), western Shandong Province. The REE-bearing carbonatite occur as veins associated with aegirine syenite. LA-ICP-MS bastnaesite Th-Pb ages (129 Ma) of the Weishan carbonatite show that the carbonatite formed contemporary with the aegirine syenite. Based on the petrographic and geochemical characteristics of calcite, the REE-bearing carbonatite mainly consists of Generation-1 igneous calcite (G-1 calcite) with a small amount of Generation-2 hydrothermal calcite (G-2 calcite). Furthermore, the Weishan apatite is characterized by high Sr, LREE and low Y contents, and the carbonatite is rich in Sr, Ba and LREE contents. The δ¹³C_V-PDB (−6.5‰ to −7.9‰) and δ¹³O_V-SMOW (8.48‰–9.67‰) values are similar to those of primary, mantle-derived carbonatites. The above research supports that the carbonatite of the Weishan REE deposit is igneous carbonatite. Besides, the high Sr/Y, Th/U, Sr and Ba of the apatite indicate that the magma source of the Weishan REE deposit was enriched lithospheric mantle, which have suffered the fluid metasomatism. Taken together with the Mesozoic tectono-magmatic activities, the NW and NWW subduction of Izanagi plate along with lithosphere delamination and thinning of the North China plate support the formation of the Weishan REE deposit. Accordingly, the mineralization model of the Weishan REE deposit was concluded: The spatial-temporal relationships coupled with rare and trace element characteristics for both carbonatite and syenite suggest that the carbonatite melt was separated from the CO₂-rich silicate melt by liquid immiscibility. The G-1 calcites were crystallized from the carbonatite melt, which made the residual melt rich in rare earth elements. Due to the common origin of G-1 and G-2 calcites, the REE-rich magmatic hydrothermal was subsequently separated from the melt. After that, large numbers of rare earth minerals were produced from the magmatic hydrothermal stage.     

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.