The lanthanide tetrad effect and its correlation with K/Rb,Eu/Eu1, Sr/Eu,Y/Ho,and Zr/Hf of evolving peraluminous granite suites

Lanthanide tetrad effects are often observed in REE patterns of more highly evolved Variscan peraluminous granites of mid-eastern Germany (Central Erzgebirge, Western Erzgebirge, Fichtelgebirge, and Northern Oberpfalz). The degree of the tetrad effect (TE_1,3) is estimated and plotted vs. K/Rb, Sr/Eu, Eu/Eu1, Y/Ho, and Zr/Hf. The diagrams reveal that the tetrad effect develops parallel to granite evolution, and significant tetrad effects are strictly confined to highly differentiated samples. Mineral fractionation as a cause for the tetrad effect is not supported by a calculated Rayleigh fractionation, which also could not explain the fractionation trends of Sr/Eu and Eu/Eu1. The strong decrease of Eu concentrations in highly evolved rocks suggests that Eu fractionates between the residual melt and a coexisting aqueous high-temperature fluid. Mineral fractionation as a reason for the tetrad effect is even more unlikely as REE patterns of accessory minerals display similar tetrad effects as the respective host rocks. The accessory minerals inherit the REE signature of the melt and do not contribute to the bulk-rock tetrad effect via mineral fractionation. These results point in summary to significant changes of element fractionation behavior in highly evolved granitic melts: ionic radius and charge, which commonly control the element distribution between mineral and melt, are no longer the exclusive control. The tetrad effect and the highly fractionated trace element ratios of Y/Ho and Zr/Hf indicate a trace element behavior that is similar to that in aqueous systems in which chemical complexation is of significant influence. This distinct trace element behavior and the common features of magmatic-hydrothermal alteration suggest the increasing importance of an aqueous-like fluid system during the final stages of granite crystallization. The positive correlation of TE_1,3 with bulk-rock fluorine contents hints at the importance of REE fluorine complexation in generating the tetrad effect. As the evolution of a REE pattern with tetrad effect (M-type) implies the removal of a respective mirroring REE pattern (W-type), the tetrad effect identifies open system conditions during granite crystallization.     

藏南错那洞淡色花岗岩成因：来自全岩地球化学和锆石U-Pb年龄的约束

藏南错那洞穹隆位于喜马拉雅造山带东部,淡色花岗岩是其核部组成部分之一。对其中的弱定向二云母花岗岩和含石榴子石二云母花岗岩进行LA-ICP-MS锆石U-Pb定年,显示其结晶年龄分别为(20.6±0.3) Ma和(16.7±0.2) Ma,属于喜马拉雅中新世淡色花岗岩。错那洞含石榴子石二云母花岗岩和弱定向二云母花岗岩均具有富硅(w(SiO2)为71.6%~74.6%)、富铝(w(Al2O3)为14.5%~16.1%)、富钾(w(K2O)为4%~4.7%)及高铝饱和指数(A/CNK=1.16~1.22)的特征,属高钾钙碱性系列的强过铝质花岗岩,并且两类花岗岩都富集Rb、U、K、Pb,相对亏损Nb、Ta、Zr、Ti。但含石榴子石淡色花岗岩具有明显的Eu负异常(Eu/Eu*=0.29~0.46),而弱定向二云母花岗岩Eu的负异常相对较弱(Eu/Eu*=0.58~0.80)。弱定向二云母花岗岩的Rb/Sr值为2.4~3.5,Ba含量为(200~253)×10-6,TiO2含量相对较低,表明错那洞弱定向二云母花岗岩是在无水条件下由变泥质岩中的白云母脱水熔融而形成,并且弱定向二云母花岗岩的产生可能与藏南拆离系(STDS)启动造成的构造减压有关。含石榴子石二云母花岗岩的K/Rb、Zr/Hf、Nb/Ta、Y/Ho值呈现出非球粒陨石异常,稀土四分组效应和异常高的Rb/Sr值(18.6~22.2)表明错那洞含石榴子石二云母花岗岩是经过岩浆高度演化而形成的。高度演化的岩浆有利于W、Sn、Be等稀有金属成矿。错那洞含石榴子石二云母花岗岩与错那洞穹隆的W-Sn-Be矿具有相邻的空间位置,两者之间可能存在一定的成因联系;而错那洞弱定向二云母花岗岩与扎西康Pb-Zn矿床在时间上和空间上都具有一致性,两者之间很可能也存在一定的成因联系。     

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

滇西含绿柱石伟晶岩锆石U-Pb年代学及其地质意义

对腾冲-梁河地区含绿柱石伟晶岩进行了锆石LA-ICP-MS U-Pb定年和地球化学分析。结果表明：含绿柱石伟晶岩的形成时代为（48.1±0.8）Ma(MSWD=4.0),锆石形态特征和微量元素特征显示,伟晶岩锆石受到热液的改造。含绿柱石伟晶岩与55~52 Ma的白云母花岗岩在主量元素、微量元素及稀土元素方面表现出极其相似的特征,为钙碱性系列,过铝质花岗岩,表现出强烈的Eu亏损,δEu为0.074~0.083,相对富集HREE,（La/Yb）_N=1.61~1.92,总体表现出典型的“M”型稀土元素四分组效应。含绿柱石伟晶岩是白云母花岗岩浆高度演化的结果,伟晶岩结晶温度为581 ℃,代表了印度-欧亚板块碰撞导致地壳加厚的构造背景。     

Tetrad effects in the rare earth element patterns of granitoid rocks as an indicator of fluoride-silicate liquid immiscibility in magmatic systems

This paper focuses on reasons for the appearance of tetrad effects in chondrite-normalized REE distribution patterns of granitoids (Li-F granites, peralklaine granites, ongonites, fluorine-rich rhyolites, and granitic pegmatites). The analysis of published data showed that the alteration of such rocks by high- and/or low-temperature metasomatic processes does not result in most cases in the appearance or enhancement of M-type tetrad effects in REE patterns. These processes are accompanied by the removal or addition of lanthanides, a W-type sag appears between Gd and Ho, and negative or positive Ce anomalies develop sometimes in REE patterns. The formation conditions of peculiar rocks enriched in Ca and F from the Ary Bulak ongonite massif (eastern Transbaikalia) and the character of REE distribution in these rocks and melt inclusion glasses were discussed. Based on the obtained data and the analysis of numerous publications, it was concluded that REE tetrad effects in rare-metal granitoids are caused by fluoride-silicate liquid immiscibility and extensive melt differentiation in the accumulation chambers of fluorine-rich magmas. A considerable increase in fluorine content in a homogeneous granitoid melt can cause its heterogenization (liquation) and formation of fluoride melts of various compositions. The redistribution of lanthanides between the immiscible liquid phases of granitoid magma will result in the formation of M-type tetrad effects in the silicate melts, because the REE patterns of fluoride melts exhibit pronounced W-type tetrad effects. The maximum M-type tetrad effect between La and Nd, which is observed in many rare-metal granitoids, is related to the character of REE partitioning between fluoride and silicate melts and F- and Cl-rich magmatic fluids. The low non-chondritic Y/Ho ratio (<15) of many rare-metal granitoids may be indicative of a contribution of fluoride melts to the differentiation of F-rich silicic magmas, from which these rocks were formed. The influence of high-temperature F-Cl-bearing fluids on melts and/or granitoid rocks results in an increase in Y/Ho ratio owing to the elevated solubility of Ho in such fluids.     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。     

Lanthanide tetrad effect in ferromanganese concretions and terra rossa overlying dolomite during weathering

The lanthanide tetrad effect was investigated in a 5.4 m thick terra rossa profile overlying dolomite on the Yunnan-Guizhou Plateau, China. The results demonstrate that the chondrite-normalized rare earth element pattern of dolomite bedrock displays a W-type tetrad effect. The insoluble residue from the dolomite bedrock does not exhibit any significant tetrad effect. In contrast, some ferromanganese concretions and the terra rossa show tetrad effect. It is worth noting that the conjugate M- and W-types of the tetrad effect are observed in some terra rossa samples. The tetrad effect in the ferromanganese concretions and the terra rossa possibly originates from redistribution of dissolved rare earth elements during their downwards movement in the profile and not only from water/rock interaction. Within the dolomite weathering system, the ferromanganese concretions and surrounding terra rossa present similar correlations of Eu/Eu*, Y/Ho, Sm/Nd, Ce/Ce*, with the size of the tetrad effect. The ferromanganese concretions and the terra rossa with tetrad effect are characterized by a reduced, non-chondritic Y/Ho ratio. Also the Y/Ho ratio exhibits a clear negative correlation with the size of the tetrad effect in the ferromanganese concretions and the terra rossa. In addition, the Eu/Eu* tends to increase with increasing size of the tetrad effect in the ferromanganese concretions and the terra rossa, as does the Sm/Nd ratio. The regular variation for Eu/Eu*, Y/Ho and Sm/Nd is likely a result of the fractionation of rare earth elements and yttrium with the tetrad effect. On the other hand, the correlation of the Ce/Ce* with the size of the tetrad effect in the ferromanganese concretions and the terra rossa is random. This likely indicates that the Ce behavior within weathering system is mainly controlled by redox condition, rather than tetrad effect. Comparative study indicates that the correlations of Eu/Eu*, Y/Ho, Ce/Ce*, with the size of the tetrad effect in the ferromanganese concretions and the terra rossa, are not similar to those found in a highly evolved igneous system. Nevertheless, the correlation of Sm/Nd with the size of tetrad effect in weathering system is similar to that in igneous system. In general, it appears to indicate that the tetrad effect occurrence in granitic rocks is not associated with weathering.     

Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho,Zr/Hf,and lanthanide tetrad effect

 The parameters which control the behaviour of isovalent trace elements in magmatic and aqueous systems have been investigated by studying the distribution of yttrium, rare-earth elements (REEs), zirconium, and hafnium. If a geochemical system is characterized by CHArge-and-RAdius-Controlled (CHARAC) trace element behaviour, elements of similar charge and radius, such as the Y-Ho and Zr-Hf twin pairs, should display extremely coherent behaviour, and retain their respective chondritic ratio. Moreover, normalized patterns of REE(III) should be smooth functions of ionic radius and atomic number. Basic to intermediate igneous rocks show Y/Ho and Zr/Hf ratios which are close to the chondritic ratios, indicating CHARAC behaviour of these elements in pure silicate melts. In contrast, aqueous solutions and their precipitates show non-chondritic Y/Ho and Zr/Hf ratios. An important process that causes trace element fractionation in aqueous media is chemical complexation. The complexation behaviour of a trace element, however, does not exclusively depend on its ionic charge and radius, but is additionally controlled by its electron configuration and by the type of complexing ligand, since the latter two determine the character of the chemical bonding (covalent vs electrostatic) in the various complexes. Hence, in contrast to pure melt systems, aqueous systems are characterized by non-CHARAC trace element behaviour, and electron structure must be considered as an important additional parameter. Unlike other magmatic rocks, highly evolved magmas rich in components such as H₂O, Li, B, F, P, and/or Cl often show non-chondritic Y/Ho and Zr/Hf ratios, and “irregular” REE patterns which are sub-divided into four concave-upward segments referred to as “tetrads”. The combination of non-chondritic Y/Ho and Zr/Hf ratios and lanthanide tetrad effect, which cannot be adequately modelled with current mineral/melt partition coefficients which are smooth functions of ionic radius, reveals that non-CHARAC trace element behaviour prevails in highly evolved magmatic systems. The behaviour of high field strength elements in this environment is distinctly different from that in basic to intermediate magmas (i.e. pure silicate melts), but closely resembles trace element behaviour in aqueous media. “Anomalous” behaviour of Y and REEs, and of Zr and Hf, which are hosted by different minerals, and the fact that these minerals show “anomalous” trace element distributions only if they crystallized from highly evolved magmas, indicate that non-CHARAC behaviour is a reflection of specific physicochemical properties of the magma. This supports models which suggest that high-silica magmatic systems which are rich in H₂O, Li, B, F, P, and/or Cl, are transitional between pure silicate melts and hydrothermal fluids. In such a transitional system non-CHARAC behaviour of high field strength elements may be due to chemical complexation with a wide variety of ligands such as non-bridging oxygen, F, B, P, etc., leading to absolute and relative mineral/melt or mineral/aqueous-fluid partition coefficients that are extremely sensitive to the composition and structure of this magma. Hence, any petrogenetic modelling of such magmatic rocks, which utilizes partition coefficients that have not been determined for the specific igneous suite under investigation, may be questionable. But Y/Ho and Zr/Hf ratios provide information on whether or not the evolution of felsic igneous rocks can be quantitatively modelled: samples showing non-chondritic Y/Ho and Zr/Hf ratios or even the lanthanide tetrad effect should not be considered for modelling. However, the most important result of this study is that Y/Ho and Zr/Hf ratios may be used to verify whether Y, REEs, Zr, and Hf in rocks or minerals have been deposited from or modified by silicate melts or aqueous fluids. Received: 4 September 1995 / Accepted: 30 October 1995     

Metasomatic crystallization of muscovite in granite and tourmaline in schist related to pegmatite emplacement near Yellowknife,Canada

Numerous pegmatite dikes occur in the Sparrow pluton (muscovite-biotite granite) and in the adjacent cordierite-zone schist-hornfels of the Yellowknife Supergroup. Where pegmatite dikes cut granite, the adjacent granite is enriched in muscovite and apatite, and depleted in K-feldspar. Mass transfer calculations, based on rock, mineral, and modal analyses, indicate that H, P, and locally B, Ti, Fe, and Ca were added, and K, Sr, Ba, and locally Na were removed (hydrogen metasomatism). In one alteration zone (8 cm wide) the calculated change (in terms of mols/gram of unaltered granite) is, 600 K-feldspar+24 biotite+190 plagioclase +[770 H+36 P+3 Ti+13 Fe+13 Ca] 400 muscovite+1100 quartz +11 apatite+[240 Na+260 K]. Where pegmatite dikes cut schist-hornfels (biotite-plagioclase-quartz), the adjacent rock is, in places, enriched in tourmaline, apatite, and quartz, and depleted in biotite and plagioclase. These alteration zones are variable in width; most are less than 20 cm wide. Mass transfer calculations, based on rock, mineral, and modal analyses, indicate that B, P, Zn, and locally Ca, Fe, and Al were added, and that Na, K, Fe, Rb, Sr, Ba, and locally Mg and Si were removed (boron metasomatism). In one zone, 2 cm wide, the calculated reaction (in units of mols/gram of unaltered schist) is, 730 biotite+1530 plagioclase +[1080 B+600 H+430 P+360 Ca] 480 tourmaline+480 quartz+115 apatite +[3630 Si+870 Na+590 K+110 Fe]. Changes in the volume fraction of muscovite, K-feldspar, tourmaline, and biotite, relative to distance from pegmatite, are progressive, and in most alteration zones may be expressed by use of an error-function equation. Some tourmaline zones are more complex. Zone formation is considered in terms of a steady-state reaction model in which grainboundary diffusion is the transport mechanism.     

Petrology and Li-Be-B geochemistry of muscovite-biotite granite and associated pegmatite near Yellowknife,Canada

Prosperous granite (Rb-Sr 2520±25 Ma) occurs as several plutons (1–380 km² outcrop area) in a thick succession of metamorphosed greywacke-mudstone of the Yellowknife Supergroup. The average mineral content of the Sparrow pluton (in vol.%) is quartz (32), plagioclase (31), K-feldspar (24), muscovite (9), biotite (3), and apatite (<1). Average trace-element concentrations (in ppm) are Li (140), Be (4), B (28), Zn (47), Rb (250), Sr (76), Zr (75) and Ba (360). The central portion of the pluton is slightly richer in K, Sr, and Ba than the margin. Li is concentrated in mica (Li in biotite/Li in muscovite=4.7), and Be and B in muscovite and plagioclase. Countless pegmatite dikes occur in the Sparrow pluton and in schist-hornfels to the east; the outer limit is marked by the cordierite isograd, 9 km from the granite contact. Dikes vary greatly in size (1 km to a few cm in length), in mineral content (quartz, albite, K-feldspar, muscovite, tourmaline, beryl, spodumene), in major element composition (especially the NaK ratio), and in trace-element content (Li 18–5000 ppm, Be 5–260 ppm, B 20–150 ppm). Compared with Prosperous granite, the pegmatite bodies are richer in P and Rb, and poorer in Ti, Fe, Mg, Zr, and Ba. Dikes rich in tourmaline, beryl, and spodumene occur in overlapping zones situated progressively farther from the centre of the Sparrow pluton. The composition of tourmaline is related to host rock; the highest concentrations of Fe and Zn occur in crystals from pegmetite and the highest concentrations of Mg and V occur in crystals from tourmalinized schist, while those from granite and quartz veins occupy on intermediate position. Complex compositional zoning is present in some tourmaline crystals in pegmatite. Estimates of temperature (500°–600° C) and pressure (2–4 kb) of granite emplacement, based on the distribution of andalusite and sillimanite in the contact rocks, suggest that the final stage of granite emplacement occurred at sub-solidus conditions. A vaportransport model is proposed to explain the widespread distribution of the pegmatite dikes and their extreme compositional variability. Some of the pegmatite constituents, including Li, Be, and B, were possibly derived from Yellowknife graywacke and mudstone.     

Trace element constraints on pegmatite genesis: Tin Mountain pegmatite,Black Hills,South Dakota

The Tin Mountain pegmatite is a small, zoned granitic body that is extremely enriched in Rb and Li, but has moderate concentrations of Sr and Ba. These trace elements are modelled using granitic distribution coefficients in order to test the potentials of partial melting of metasedimentary rocks and fractionation of a less-evolved granitic melt to have produced the parental liquid to the Tin Mountain pegmatite. Batch melting of any reasonable metasedimentary source rock would likely have yielded melts that were either insufficiently enriched in Rb and Li to be the parental liquid, or that had Sr and Ba concentrations that were much higher than those estimated for the parental liquid. The modelling of simple fractional crystallization and equilibrium crystallization of a granitic melt within the compositional range of the spatially associated Harney Peak Granite gives calculated melt compositions with either lower Sr and Ba concentrations or inadequate Rb and Li enrichments, to be the parent liquid of the pegmatite. At least two variants from simple crystal-liquid fractionation models can, however, successfully account for the derivation of the parent liquid: 1) generation of a Rb-, Li-, Ba- and Sr-rich granitic melt (outside of the compositional range of the sampled portions of the Harney Peak Granite complex) by low degrees of partial melting of metasedimentary rocks found in the Black Hills, followed by moderate extents of fractional or equilibrium crystallization, 2) derivation from Harney Peak granite via a complex, multi-stage crystal-liquid fractionation process, such as progressive equilibrium crystallization.     

Trace element geochemistry by laser ablation ICP-MS of micas associated with Ta mineralization in the Tanco pegmatite,Manitoba, Canada

In the Tanco pegmatite, one of the world’s major Ta deposits, tantalum mineralization shows a complexity that reflects the complex petrogenesis of its host pegmatite. Micas are common in most of the pegmatite units and are intimately associated with the successive stages of Ta mineralization, from the wall zone to the central zones where micaceous replacement is pervasive. Different generations of micas, both primary and secondary, associated with Ta oxides, were selected for electron microprobe and laser ablation ICP-MS investigation. Their chemical trends are used to constrain the magmatic versus hydrothermal processes that played a role in their crystallization and their associated Ta mineralization. Micas range from dioctahedral muscovite to trioctahedral lepidolite through Al↔Li substitution. Unexpectedly, the most evolved compositions (low K/Rb ratios and high Li contents) occur in the wall zone; they are interpreted to reflect nonequilibrium crystallization from an undercooled melt, with or without boundary layer effects. In the central zones, the fine-grained mica–quartz assemblage hosts some coarser-grained Li-muscovite, which has the highest Ta contents (up to 400 ppm). These Li–F–a-rich micas are interpreted to originate from a magmatic metasomatic event, which was also at the origin of the MQM-style Ta mineralization at Tanco. However, the Li–Ta-poor, muscovite end-member compositions of fine-grained alteration micas suggest crystallization from an aqueous fluid, during a metasomatic (hydrothermal) event involving late pegmatitic fluids. The low Ta concentrations (around 50 ppm) of this fine-grained muscovite suggest that this fluid transported at least small amounts of Ta.     

川西扎乌龙-青海草陇花岗伟晶岩型稀有金属矿床磷灰石地球化学特征及地质意义

扎乌龙-草陇锂矿床位于松潘-甘孜造山带中西部,为典型的花岗伟晶岩型稀有金属矿床.前人基于矿区花岗岩和伟晶岩紧密的时空及成因关系,认为伟晶岩与白云母花岗岩同源且成矿与花岗质岩浆的分异相关.然而,岩浆分异演化过程中熔体的信息记录及其何种地质过程对成矿起主导作用,仍缺乏有效制约.本文对矿区花岗质岩浆来源及其演化过程开展了研究...     

The Lanthanide Tetrad Effect in Argillic Alteration: An Example from the Jizvan District,Northern Iran

Intrusion of quartz‐monzodioritic igneous bodies of Oligocene age into Eocene lithic crystal tuffs and trachy‐basalts resulted in the occurrence of a widespread argillic alteration zone in the Jizvan district (northern Iran). Mineralogically, the argillic alteration zone includes minerals such as kaolinite, quartz, smectite, pyrophyllite, muscovite‐illite, alunite, rutile, calcite, feldspar, chlorite, hematite and goethite. Therefore, the non‐CHARAC behaviour for trace elements in the argillic samples is reflected in the non‐chondritic Y/Ho and Zr/Hf ratios and the irregular REE patterns, which appear related to the tetrad effect phenomenon. The chondrite‐normalized REE distribution patterns indicate both concave (W‐shaped) and convex (M‐shaped) tetrad effects in the argillic samples. Based on the field evidence and the results from geochemical studies, it can be concluded that the samples from the argillic alteration zone having high fourth tetrad effect values (>0.30) were developed in the fault and breccia zones. The results indicate that factors such as preferential scavenging by Mn‐oxides, crystallization of clay minerals, fluid‐rock interaction, overprint of hypogene mineral assemblage by supergene ones, and the structural control, have all played an important role in the occurrence of tetrad effects in samples of the argillic zone in the Jizvan district.     

白云母成分对富锂铍伟晶岩成因的指示：以卡鲁安稀有金属矿田为例

新疆阿尔泰造山带是我国重要的稀有金属矿床矿产资源基地,尤以富Li和富Be伟晶岩型矿床广泛发育为特色。本研究选择阿尔泰造山带卡鲁安-阿祖拜矿田富Li和富Be伟晶岩型矿床开展典型解剖,以贯穿岩浆阶段-伟晶岩阶段的白云母矿物为研究主线,探讨不同矿化类型伟晶岩中云母的成分演化规律、花岗岩与伟晶岩的成因联系。矿物学特征显示富Be伟晶岩中发育大量磷酸盐矿物,而富Li伟晶岩含较多橙色锰铝榴石、锂云母而缺乏典型的Fe-Mn磷酸盐。白云母成分分析显示,从白云母花岗岩→富Be伟晶岩→富Li伟晶岩,白云母总体呈Nb含量和Nb/Ta值降低,指示白云母花岗岩、富Be伟晶岩经历了不同程度的分离结晶作用,也代表了富Li伟晶岩的岩浆分异演化程度更高。尽管利用云母成分变化(尤其是K、Rb、Cs等大离子亲石元素)模拟岩浆结晶演化过程,显示可由初始花岗质岩浆经瑞利分离结晶作用依次形成白云母花岗岩→富Be伟晶岩→富Li伟晶岩的假设。但研究区年代学、矿物学、同位素证据指示富Li伟晶岩和富Be伟晶岩具有不同的熔体性质和形成时代。因此,应用云母成分探讨伟晶岩的成因联系应当建立在花岗岩-伟晶岩系统具有合理的时空分布和其它支持源自同一...     

新疆阿尔泰可可托海伟晶岩型稀有金属矿床中磷灰石地球化学特征及意义

磷灰石可以记录和保存岩浆和热液活动的信息。可可托海伟晶岩型稀有金属矿床磷灰石发育,为研究该矿床伟晶岩成岩成矿过程提供了优良的条件。已有对可可托海伟晶岩型稀有金属矿床磷灰石的研究集中在其稀土元素特征,较少讨论其对伟晶岩成岩成矿过程的制约。本文选取可可托海伟晶岩型稀有金属矿床富矿伟晶岩脉(3号脉)和相对贫矿伟晶岩脉(1号、2b号和3a号脉)中的磷灰石作为研究对象,进行磷灰石岩相学和地球化学研究。岩相学分析表明,磷灰石主要与钠长石、石英、白云母、锰铝榴石等伴生。EPMA分析显示,磷灰石F含量为3.67%～4.41%,Cl含量小于0.67%,较低的Cl含量表明伟晶岩熔体出溶的流体Cl含量较低;大部分磷灰石MnO含量为4.67%～8.71%,但2b号脉磷灰石MnO含量变化较大(1.23%～14.28%),这是由于2b号脉磷灰石具有分带结构,暗示其遭受后期热液作用,促使磷灰石溶解-再沉淀,导致MnO含量发生较大变化。LA-ICP-MS分析显示,贫矿伟晶岩脉磷灰石的稀土元素含量较低(180×10~(-6));相反,富矿伟晶岩脉磷灰石的稀土元素含量较高( 700×10~(-6)),并具有明显的四分组效应(TE_(1-3)平均值为1.7)。1号脉和3a号脉磷灰石均显示轻稀土元素富集,反映其形成过程中有含Cl热液的参与。3号脉磷灰石显示强烈Eu负异常和Ce正异常,而2b号脉磷灰石显示强烈Ce负异常和中等Eu负异常,这种Eu、Ce异常的差异可能与岩浆-热液阶段大量流体出溶密切相关。磷灰石的沉淀将导致热液中HF含量的降低,促使磷灰石周围铌钽矿结晶和Nb、Ta进入磷灰石中。可见,在伟晶岩形成过程中,磷灰石并非保持稳定,其分带结构和主微量成分变化记录了后期热液活动,暗示后期热液活动对伟晶岩的成矿具有重要作用。     

Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks

Some F-rich granitic rocks show anomalous, nonchondritic ratios of Y/Ho, extreme negative Eu anomalies, and unusual, discontinuous, segmented chondrite-normalised plots of rare earth elements (REE). The effects of F-rich fluids have been proposed as one of the explanations for the geochemical anomalies in the evolved granitic systems, as the stability of nonsilicate complexes of individual rare earths may affect the fluid-melt element partitioning. The lanthanide tetrad effect, related to different configurations of 4f-electron subshells of the lanthanide elements, is one of the factors affecting such complexing behaviour. We present the first experimental demonstration of the decoupling of Y and Ho, and the tetrad effect in the partitioning of rare earths between immiscible silicate and fluoride melts. Two types of experiments were performed: dry runs at atmospheric pressure in a high-temperature centrifuge at 1100 to 1200°C, and experiments with the addition of H₂O at 700 to 800°C and 100 MPa in rapid-quench cold-seal pressure vessels. Run products were analysed by electron microprobe (major components), solution-based inductively coupled plasma mass spectrometry (ICP-MS) (REE in the centrifuged runs), and laser ablation ICP-MS (REE and Li in the products of rapid-quench runs). All the dry centrifuge runs were performed at super-liquidus, two-phase conditions. In the experiments with water-bearing mixtures, minor amounts of aqueous vapour were present in addition to the melts. We found that lanthanides and Y concentrated strongly in the fluoride liquids, with two-melt partition coefficients reaching values as high as 100-220 in water-bearing compositions. In all the experimental samples, two-melt partition coefficients of lanthanides show subtle periodicity consistent with the tetrad effect, and the partition coefficient of Y is greater than that of Ho. One of the mixtures also produced abundant fluorite (CaF₂) and cryolite (Na₃AlF₆) crystals, which enabled us to study fluorite-melt and cryolite-melt REE partitioning. REE concentrations in fluorite are high and comparable to those in the fluoride melt. However, fluorite-melt partition coefficients appear to depend mostly on ionic radii and show neither significant tetrad anomalies, nor differences in Y and Ho partitioning. In contrast, REE concentrations in cryolite are low (∼5-10 times lower than in the silicate melt), and cryolite-melt REE partitioning shows very strong tetrad and Y-Ho anomalies. Our results imply that Y-Ho and lanthanide tetrad anomalies are likely to be caused mainly by aluminofluoride complexes, and the tetrad REE patterns in natural igneous rocks can result from fractionation of F-rich magmatic fluids.     

福建南平花岗伟晶岩型钽铌矿床地质特征与成因

福建南平钽铌矿是亚洲最大的花岗伟晶岩型钽铌矿床,也是中国钽铌金属矿的重要产地。南平钽铌矿在构造上位于闽西北隆起带东南缘,矿区内广泛发育有中—新元古界变质岩系。钽铌矿多呈脉体,沿变质岩系的片理或层理侵入,矿脉与围岩的关系清晰。这些脉体是在与加里东期花岗岩有成因联系的4类花岗伟晶岩分异—演化的基础上形成的。矿化伟晶岩中分带和交代蚀变作用均十分发育,稀土元素的矿化与伟晶熔体的结晶分异及后期热液蚀变作用有较密切的关系。稀土元素和磷酸盐矿物含量很多,这在国内外同类型伟晶岩中不常见。同时该地区也是新矿物——南平石的唯一产地。钽铌矿物是矿化伟晶岩中Ta和Nb元素的最主要载体,Ta含量大于Nb,还有其他可综合利用的稀土元素。闽西北地区具有进一步寻找此类型矿化伟晶岩的广阔前景。     

川西甲基卡花岗伟晶岩型锂矿床中熔体、流体包裹体固相物质研究

川西甲基卡二云母花岗岩和伟晶岩内发育大量原生熔体包裹体和富晶体流体包裹体。为了查明甲基卡成矿熔体、流体性质与演化特征,运用激光拉曼光谱和扫描电镜鉴定了甲基卡花岗伟晶岩型锂矿床中二云母花岗岩及伟晶岩脉不同结构带内的原生熔体、流体包裹体的固相物质。分析结果表明,甲基卡二云母花岗岩石英内熔体包裹体的矿物组合为磷灰石+白云母、白云母+钠长石、白云母+石墨;伟晶岩绿柱石内富晶体流体包裹体的矿物组合主要为刚玉、富铝铁硅酸盐+刚玉+锂辉石、锂辉石+石英+锂绿泥石;伟晶岩锂辉石内富晶体流体包裹体的矿物组合主要为磷灰石、锡石、磁铁矿、石英+钠长石+锂绿泥石、萤石、富钙镁硅酸盐+富铁铝硅酸盐+富铁硅酸盐+石英;花岗岩浆熔体与伟晶岩浆熔体(流体)具有一定的差异,成矿熔体、流体成分总体呈现出碱质元素(Na、Si、Al)、挥发分(F、P、CO_2)含量增高及基性元素(Fe、Mg、Ca)降低的特征;包裹体中子矿物与主矿物的化学成分具有一定的差别,揭示出伟晶岩熔体(流体)存在局部岩浆分异作用,具不混溶性及非均匀性。因此认为,伟晶岩熔浆(流体)为岩浆分异与岩浆不混溶共同作用的产物,挥发分含量的增高(F、P、CO_2)使伟晶岩能够与稀有金属组成各类络合物或化合物,这对于稀有金属成矿起到了至关重要的作用。     

Topaz–albite granites and rare-metal mineralization in the Limu District, Guangxi Province, southeast China

The topaz-albite granites of the Limu district are ultra-acidic, peraluminous, Li-F-Na-rich and Sn-Ta-Nb-mineralized. A distinct vertical zonation is developed in the granite stocks. There is an upward, systematic transition from leucocratic microcline-albite granite, through albite-microcline granite, topaz-albite granite, pegmatite stockscheider and layered pegmatite-aplite dikes, to K-feldspar-quartz veins and lepidolite-fluorite stringers in the country rocks. Snow-ball textures, homogeneous distribution of rock-forming and accessory minerals, disseminated mineralization, and melt inclusions in quartz, topaz, and albite are typical features indicative of their crystallization from the late stage Li-F-Na-rich and Sn-Ta-Nb-bearing residual granitic melts at a higher intrusion level. A comparison with rare-metal-bearing pegmatite, ongonite, topaz rhyolite and obsidian glass from other regions shows the worldwide existence of these specialized residual melts. Their emplacement and crystallization in a variety of geological environments result in the formation of a series of chemically similar rocks with different petrographic textures and mineral associations. The topaz-albite granites and associated mineralization in the Limu district provide a good example of highly evolved magmatic fractionation in the F-rich granite system and fluid/melt partitioning behavior of rare-metal elements during magmatic-hydrothermal evolution.