Differential Fractionation of Rare Earth Elements in Oxidized and Reduced Granitic Rocks: Implication for Heavy Rare Earth Enriched Ion Adsorption Mineralization

Ion adsorption rare earth element (REE) deposits in southern China are the exclusive source of heavy REEs (HREEs) in the world, and this HREE‐enriched character of the deposits is inherited from the REE compositions of the underlying granitic rocks. Such HREE‐enriched rocks form from heavy fractionation of reduced granitic magmas. We explore why reduced granitic magmas are enriched in HREEs during the fractionation, based on the REE geochemistry of granitic rocks and abundance of REEs in their constituent minerals in the southwestern Japan arc of Cretaceous to Paleogene age. The compilation of the whole rock geochemistry and REE compositions of the granitic rocks of the Sanin (oxidized), Sanyo (reduced) and Ryoke (reduced) belts in the southwestern Japan arc indicates that: (i) light REEs (LREEs) decease with fractionation of the granitoids in the Sanin belt but this trend is not clear in the granitoids in the Sanyo belt and LREEs rather increase in the Ryoke granitoids; (ii) Eu decreases with fractionation in all the belts; and (iii) HREEs slightly, but steadily decrease in the Sanin belt but enrich significantly in the Sanyo and Ryoke belts with fractionation. Analytical results of REE concentrations by scanning electron microscope with energy dispersive X‐ray spectroscope and laser ablation‐inductively coupled plasma mass spectrometer in the constituent minerals in a granodiorite sample from the Sanin belt show a moderate concentration of REEs in hornblende (577 ppm) in addition to high concentrations in allanite (~20 %), britholite (~30 %), primary titanite (8922 ppm), apatite (4062 ppm), and zircon (1693 ppm). Because primary titanite and allanite are commonly present in the oxidized granitoids but not in the reduced ones, the REE depletion in the fractionated, oxidized granites is attributed to the crystallization of these minerals. In contrast, scarcity of these minerals in the reduced granitoids enriches REEs, in particular HREEs in the fractionated magmas, which finally precipitate REEs in the granites and pegmatites. Both positive, but different correlation ratios between the Nb and Dy concentrations in the granitoids of the Sanin and Sanyo‐Ryoke belts suggest that columbite–pyrochlore‐group and fergusonite‐group minerals are the major HREE host in the oxidized and reduced granites, respectively.     

北山柳园地区双峰山早泥盆世A型花岗岩的确定及其构造演化意义

北山柳园地区分布有大量的早中古生代花岗岩类岩石.柳园双峰山岩体具有高硅、高碱(AR=3.99～5.05,NK/A>0.85)、高FeOT/MgO比值和10 000×Ga/Al值、低Al2O3、贫CaO和MgO的特征,显示出准铝质、碱质花岗岩的特点;∑REE较高,LREE略富集,轻重稀土元素分馏不十分明显,Eu负异常明显;相对富集Rb、K、Pb等大离子亲石元素(LILE),强烈亏损Ba、Sr、P、Eu、Ti,弱亏损Ta、Nb等元素;同时具有较高的Rb/Nb和Y/Nb比值,显示了A2型铝质花岗岩的特征.采用LA-ICP-MS锆石U-Pb定年方法,获得双峰山岩体的206Pb/238U年龄为415±3 Ma(MSWD=1.5),代表该岩体的形成年龄,即双峰山岩体形成于早泥盆世.地球化学及Nd同位素特征综合分析显示,该岩体可能由幔源岩浆底侵导致上覆地壳物质(可能由洋壳和岛弧建造组成)部分熔融形成的花岗闪长质岩浆经进一步结晶分异作用形成,为该区较早的钙碱性花岗岩演化到后期的产物.岩体特征、年代学、地球化学和地质背景综合分析结果表明,该岩体形成于后造山或造山作用演化晚期阶段.双峰山早泥盆世A型花岗岩为目前北山地区发现的最老的A型花岗岩,这对探讨古生代花岗岩成因类型及岩浆演化具有重要的意义.     

A型花岗岩的微量元素地球化学

本文总结和评述了A型花岗岩典型的微量元素特征,如富集Ga、稀土元素（除Eu外）和高场强元素,亏损Ba、Sr和明显的Eu负异常。分别讨论了影响微量元素特征的多种制约因素,主要包括源区性质、岩浆的物理化学条件、岩浆作用过程和络合作用。通过对比世界范围内几个地区相伴生的碱性A型花岗岩和铝质A型花岗岩的微量元素地球化学特征,发现前者Ga、F含量更高,而轻重稀土比值小,Eu、Ba、Sr等元素含量更低,显示了前者的岩浆分异作用更强,同时说明了碱性A型花岗岩可以由与之伴生的铝质A型花岗岩分异而来。     

秦岭蟒岭高Sr花岗岩的锆石Lu-Hf同位素特征及其成因

蟒岭花岗岩体位于商丹构造带北侧的北秦岭构造带上,为一呈近东西走向的中生代花岗岩基。蟒岭花岗岩属高钾钙碱性—钾玄岩系列、过铝质I型花岗岩,其w(SiO2)=67.3%～73.7%,w(Al2O3)=14.0%～16.3%,w(Na2O)=3.17%～3.93%、w(K2O)=3.9%～6.3%,具高Sr、Ba、LREE、Sr/Y、La/Y,低HREE、Y、Mg#(50)、Rb/Sr,亏损Nb、Ta、Ti和P,无明显负Eu异常的特征,与中国东部的高Sr、Ba低HREE花岗岩的地球化学特征相似。锆石εHf(t)值为-9.4～-3.1,二阶段模式年龄(tDM2)集中于1.4～1.8 Ga,暗示蟒岭高Sr花岗岩的原岩主要为中新元古代地壳物质,并混入少量幔源物质;源区残留石榴石,而角闪石、斜长石为主要熔融相。蟒岭高Sr花岗岩形成于陆内造山阶段,由增厚的下地壳物质发生减压部分熔融形成,而底侵的镁铁质岩浆可能为部分熔融作用提供了热量。     

佛冈高分异I型花岗岩的成因:来自Nb-Ta-Zr-Hf等元素的制约

华南南岭地区发育有大面积的与钨锡成矿相关的侏罗纪花岗岩,然而其中有些花岗岩的成因类型却难以确定。本文以佛冈岩体为例,结合前人已发表数据,对佛冈花岗岩体中Nb、Ta、Zr和Hf等元素的迁移特征及其原理进行探讨,并对佛冈花岗岩的成因类型进行了厘定。随着分异程度增加,佛冈花岗岩Nb和Ta含量增加,Nb/Ta(3.6~15.3)和Zr/Hf(17.3~38.9)比值降低并发生分异。随着Zr含量的降低,佛冈花岗岩的Zr/Hf比值降低,这一特征表明锆石的分离结晶作用使得佛冈花岗岩的Zr/Hf比值分异。Nb/Ta比值分异可能与角闪石和黑云母的分离结晶作用有关。随着Nb/Ta比值降低,Y/Ho比值增加,这一特征表明佛冈花岗岩Nb/Ta比值的分异也和岩浆演化后期的流体有关。佛冈花岗岩不含原生的富铝矿物,为准铝质到弱过铝质岩石。随着分异程度增加,佛冈花岗岩P2O5含量降低,表明它不是S型花岗岩。随着Y/Ho比值增加和Nb/Ta和Zr/Hf比值降低,佛岗花岗岩Ga/Al和Fe OT/Mg O比值增加,从典型I型花岗岩特征演化到类似A型花岗岩的地球化学特征。因此,我们认为佛冈花岗岩不是A型花岗岩而是高分异的I型花岗岩。区域上与成矿相关的流体和花岗质岩浆的相互作用和分离结晶作用,使得华南南岭地区的花岗岩地球化学特征复杂,所以其成因类型也变的难以确定。     

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

湖南香花岭地区花岗岩中锂对成岩成矿的制约

锂(Li)是一种战略关键金属,岩浆阶段主要在花岗质岩石中得到富集和结晶.由于具有不相容和富挥发性等性质,锂对花岗岩的成岩成矿具有重要的制约.文章利用电子探针、LA-ICP-MS等分析手段,对湖南香花岭地区癞子岭和尖峰岭花岗岩进行系统岩相学、主微量和矿物学研究,结果表明:(1)花岗质岩浆结晶分异过程中,Li含量逐渐升高,...     

大兴安岭诺敏地区二叠纪花岗岩的地球化学特征及地质意义

大兴安岭诺敏地区大地构造位置位于兴蒙造山带的东段.该区发育大量的二叠纪花岗岩类岩石,岩性主要为二长花岗岩、钾长花岗岩.岩石地球化学分析结果表明,该区岩体具有高硅,略富铝,偏碱,低镁、钠,贫钙的特征.微量元素表现出富集Rb、Th、K、Nd、Cs和亏损U、Nb、Sr、P、Ti等特点;稀土元素具有明显的轻稀土元素富集、重稀土元素亏损和明显的负Eu异常特征.轻重稀土元素分馏程度较强.岩石总体上属于高钾钙碱性系列花岗岩.地球化学特征表明其应为S型花岗岩,可能为同源的地壳物质的部分熔融作用所形成,源岩可能为变杂砂岩和变中性火山岩.根据R1-R2与Rb-（Yb+Nb）、Rb-（Yb+Ta）等微量元素判别图解,结合该区所处的构造环境推测,该区花岗岩应形成于兴安地块与松嫩地块碰撞造山过程的后碰撞阶段.     

南岭地区钨锡铌钽花岗岩及其成矿作用

在晚侏罗世时,南岭地区发生了与花岗岩有关的钨锡铌钽大规模成矿作用。依据花岗岩的岩石学、地球化学及其矿化特征,可将南岭地区含钨锡铌钽花岗岩划分为三个主要类型：含钨花岗岩、含锡钨花岗岩和含钽铌花岗岩。含钨花岗岩的地球化学特征可归纳为铝过饱和,低Ba+Sr 和TiO2,轻重稀土比值低,铕亏损强烈,富Y 和Rb,Rb/Sr 比值高,分异强烈。含锡钨花岗岩总体特征表现为TiO2 含量高,准铝质—弱过铝质,轻重稀土比值和CaO/(K2O+Na2O)比值高,富高场强元素、稀土、Ba+Sr 和Rb,低Rb/Sr 比值,分异演化程度较低。含钽铌花岗岩的地球化学特征主要为TiO2 含量和CaO/(K2O+Na2O)比值低,Al2O3/TiO2 和Rb/Sr 比值明显偏高,强过铝质,贫Ba+Sr、稀土和高场强元素,铕亏损强烈,明显富Rb 和Nb,高度分异演化。三类含矿花岗岩具有明显不同的演化特征,成矿作用与它们的演化密切相关。黑云母花岗岩主要与锡成矿作用有关,二云母花岗岩和白云母花岗岩主要产生钨矿化或锡钨共生矿化,钠长石花岗岩主要与钽铌或锡（钨）钽铌矿化有关。总结了南岭锡钨钽铌矿床的重要类型,提出了绿泥石化花岗岩型锡矿新类型,指出南岭地区要特别注意在含锡钨花岗岩中寻找此类锡矿和云英岩- 石英脉型锡钨矿。     

Evolution of Pan African A- and I-Type Granites from Southeastern Egypt: Inferences from Geology,Geochemistry, and Mineralization

Field study of granitic rocks in the Gebel Abu Brush-Dahis (ABD) area, Southeastern Desert, Egypt, shows that they comprise two granitic groups, namely A- and I-type suites. The A type is distinguished mineralogically by abundant orthoclase and sodic plagioclase, ferrohornblende, monazite, and allanite. In contrast, the I type has more hornblende and biotite, which are more magnesian in composition, and less feldspar. The parental magmas of both suites have many similar geochemical characteristics, although the A type has slightly higher alkalis, Zr, Hf, Zn, and LREE, and lower CaO, MgO, Sr, Ni, and Fe⁺². The geochemical properties characteristic of leucocratic A-type granites-such as high Ga/Al ratios, Nb, Y, HREE, and F contents-are only manifest in the more felsic members of the A-type suite. These features were produced by 70% fractional crystallization of feldspar, hornblende, quartz, and biotite. Geotectonically, the study revealed that the A-and I-type granites are typical of an arc setting, but the more felsic members of the A-type suite plot in a within-plate regime. Geochemically, the granites are subalkaline and peraluminous to metaluminous. The granodiorites/adamellites (I-type suite) have fractionated LREE and slightly fractionated or nearly flat HREE, with small or no Eu anomalies. The alkali-feldspar granites (A-type suite) have flat REE with large Eu anomalies, except for one sample, which shows increasing LREE and decreasing HREE with large Eu anomalies; the quartz-monzonites have fractionated LREE and nearly flat HREE with no Eu anomaly. The flat HREE and/or HREE enrichment is attributed to involvement of garnet and/or zircon in melt generation at the source.

The uranium and thorium contents in the granitic rocks are present in the accessory minerals—particulary in monazite, titanite, zircon, allanite, fluorite, apatite, and opaques. Anomalous high radioactivity in the bostonite (alkaline) dike as well as uranium mineralization are largely confined to contacts and fracture zones. Uranophane is the characteristic uranium mineral in the oxidation zone. An XRD study of the high anomalies in pegmatite and bostonite reveals that the uranium mineralizations produced uranophane (Usilicate), thorianite, soddyite, zippeite, and becquerelite.     

湘东北新元古代强过铝花岗岩的成因：年代学和地球化学证据

湘东北新元古代强过铝(SP)花岗岩主要由长三背和大围山两个岩体组成,它们的ASI值平均为1.24,LREE 富集,HREE 较为平坦,Eu/Eu~* 平均为0.51,Ba、Nb、Ta、Ti、P亏损,K、Rb、Th 富集,具有S型花岗岩的特征。长三背岩体单颗粒锆石蒸发法~(207)Pb/~(206)Pb 年龄为929±6 Ma,其较老的 Nd模式年龄、2491±2 Ma 残留锆石的年龄表明该地区可能存在新太古代—古元古代的基底。这些花岗岩 CaO/Na_2O 值>0.3,来源于富砂屑质的中元古代冷家溪群浅变质岩的部分熔融,所处的造山带与拉克伦褶皱带一样属于高温型碰撞带。该地区及江南造山带中其他同时代SP花岗岩的带状分布表明它们与地幔柱的活动无关,而是华夏和扬子地块相互碰撞的产物。湘东北花岗岩中镁铁质微花岗岩类包体及岩体附近闪斜煌斑岩的存在,表明其形成可能有基性物质的参与。这些花岗岩属后碰撞花岗岩,其热源可能由俯冲板片裂离导致的软流圈基性岩浆底侵所提供,岩浆上升过程捕获围岩物质,并在地壳中—浅层侵位。     

Pan-African Alkali Granitoids from the Sør Rondane Mountains, East Antarctica

Alkali granitoids (500-550 Ma) representing a prominent Pan-African magmatic event are widely distributed in the Sør Rondane Mountains, Dronning Maud Land, East Antarctica. Geochemically, they are granitic to syenitic in composition and show an alkaline affinity of A-type granites. They are characterized by high K₂O+Na₂O (7-13 wt%) and K₂O/Na₂O (1-2), low to intermediate Mg#, wide ranges of SiO₂ (45-78 wt%), Sr (20-6500 ppm) and Ba (40-13000 ppm) and have Nb and Ti depletion in the primitive mantle normalized diagram. The granitoids are subdivided into Group I granites, Group II granites, Lunckeryggen Syenitic Complex and Mefjell Plutonic Complex. The Group I granites have higher Mg#, Sr/Ba, Sr/Y, (La/Yb)_N and LREE/HREE, lower A/CNK, SREE and initial ⁸⁷Sr/⁸⁷Sr ratios and lack Eu anomalies compared to those with negative Eu anomalies in the Group II granites. The syenitic rocks from the Mefjell Plutonic Complex are higher in alkali, Ga, Zr, Ba, and have lower Mg#, Rb, Sr, Nb, Y, F and LREE/HREE with positive Eu anomaly, whereas the granites from the Mefjell Plutonic Complex have high LREE/HREE ratios with negative Eu anomaly. The Lunckeryggen syenitic rocks have intermediate Mg#, higher K₂O, P₂O₅, TiO₂, Fe₂O₃/FeO, Ba, Sr/Y and LREE/HREE ratios with lack of Eu anomalies and are lower in Al₂O₃, Ga, Y, Nb and Rb/Sr ratios. Based on chemical characteristics combined with isotopic data, we suggest that the Lunckeryggen syenitic body and Group I granitic bodies may be derived from the mantle-derived hot basic magma by fractional crystallization with minor assimilation. We also suggest that the Group II granites may be derived from assimilation with crustal rocks to varing degrees and then fractional crystallization in higher crustal levels (ACF model). The Mefjell Plutonic Complex seems to be derived from a heterogenetic magma source compared with other granitoids from the Sør Rondane Mountains. The syenitic rocks in the Mefjell Plutonic complex have a unique source (iron-enriched) and have a chemical affinity with the charnockites in Gjelsvikjella and western Mühlig-Hofmannfjella, but not like the Yamato syenites in adjacent areas.     

Proterozoic Metamorphic Rock-Hosted ZR,Y, and HREE Mineralization in the Dabie Mountain Area,Central China

Zr, Y, and heavy rare earth element (HREE) mineralization hosted by late Proterozoic metamorphic rocks from the western Dabie Mountains, northern Hubei Province, central China was discovered in 1978 by the Hubei Regional Geological Party (Li et al., 1981) and is examined further in this paper. The area is located in the EW-trending fold belt between the Sino-Korean and Yangtze cratons. Highly metamorphosed hornblende-plagioclase gneiss, granitic gneiss, and migmatites of the late Archean Dabie Group constitute the basement, which is unconformably covered by the late Proterozoic Hongan Group—a sequence of phosphorus-bearing layer(s), dolomitic marbles, muscovite-albite schist, felsic schists, and a variety of greenschists.

The stratiform Zr, Y, and HREE mineralization is hosted by felsic and albite-muscovite schists of the lower part of the Hongan Group, which was highly stressed and deformed. The mineralized layer, about 10 m in thickness, occurs concordantly in the strata and extends discontinuously more than 15 km from northwest to southeast. The host felsic schists have a mineral assemblage of quartz + albite + microcline + muscovite + magnetite ± epidote ± garnet, and are estimated to have been subjected to a metamorphism of 3607–440 °C. Accessory minerals include zircon, gadolinite, fergusonite, xenotime, monazite, allanite, gahnite, and apatite. The rocks are very similar to metaluminous rhyolite in major component composition: they are moderately to highly enriched (ppm) in Zr (4980–6246), Y (745–1119), Nb (186–232), Ta (18–24), Th (132–171), U (22–28), Yb (83–109), Hf (183–204), Ga (35–50) and Sn (39–48) and have relatively high Rb/Sr ratios (6–17). These chemical features are, to a certain extent, similar to those of high-silica rhyolites from North America, and comparable to H?gtuva Be-REE-U-Sn-mineralization in Precambrian granitic gneiss in Norway, to a volcanic-hosted rare-metals deposit at Brockman, Western Australia, and to Zr, Nb, Y, and HREE mineralization related to alkaline and peralkaline granites from Canada, the Arabian Shield, Nigeria, and northern China. A submarine sedimentary-volcanic origin is proposed for interpretation of the genesis of this unusual HREE mineralization.     

Geochemistry of granulite‐facies granitic rocks from Battye Glacier,northern Prince Charles Mountains,East Antarctica

Proterozoic basement outcrops in the vicinity of Battye Glacier, northern Prince Charles Mountains, are dominated by granulites and gneisses derived from felsic (granitoid) intrusive igneous rocks, and by pegmatites. Felsic orthopyroxene granulites, garnet leucogneisses and garnet pegmatites have major and trace element compositions of highly felsic, but not strongly fractionated, granites. The garnet leucogneisses and garnet pegmatites have S‐type characteristics, whereas the felsic granulites are probably I‐type, although their high Zr+Nb+Y+Ce abundances suggest possible A‐type affinities. Intermediate orthopyroxene ± clinopyroxene granulites mostly resemble I‐type quartz diorites, except for a small subgroup of samples (characterised by low Na₂O and K₂O, and high MgO, Ni, Cr and HREE) of uncertain affinities and significance. Element ratios involving LILE (e.g. K/Rb, Rb/Ba, Rb/Sr, K/La, La/Th) closely match those typical of the inferred granitoid protoliths, suggesting that these rocks have experienced relatively little LILE depletion (except possibly for U) during regional metamorphism. It is therefore inferred that metamorphism was probably broadly isochemical. Because the felsic and intermediate granulites and garnet leucogneisses are Sr‐depleted, Y‐undepleted and mostly have negative Eu anomalies they are inferred to be the products of partial melting of felsic crustal sources leaving plagioclase‐bearing residua. Plagioclase fractionation during crystallisation could also account for these characteristics, but K/Rb, Rb/Ba and Rb/Sr ratios in these rocks are not consistent with strong fractionation of feldspar. Garnet pegmatites differ chemically from garnet leucogneisses mainly in their lower Fe, Ti, Nb, Zn, Zr, Th and REE abundances and positive Eu anomalies, related to lower garnet, ilmenite and zircon contents in the garnet pegmatites. A genetic link between these two rock types, probably involving fractionation of these minerals during partial melting or crystallisation, is inferred. Incompatible‐element abundances suggest that generation of the Battye Glacier granitic magmas from felsic crust might have occurred in a mature continental magmatic arc possibly well removed from an active subduction trench or, perhaps, in an intracontinental setting.     

柴北缘锡铁山花岗斑岩锆石U—Pb年代学、地球化学及Hf同位素

对锡铁山北东侧的花岗斑岩体进行锆石U—Pb年代学、岩石地球化学及Hf同位素研究。通过LA—ICP—MS锆石U—Pb同位素测年,获得花岗斑岩的成岩年龄为373. 9±2. 2 Ma (MSWD=0. 069),属于晚泥盆世岩浆活动的产物。岩石地球化学特征显示岩石富硅(SiO_2=76. 33%～76. 99%)和碱(K_2O+Na_2O=7. 28%～8. 19%),低钙(CaO=0. 58%～0. 75%)、镁(MgO=0. 20%～0. 31%)和Mg~#值(Mg~#=23. 29～30. 17),A/CNK介于0. 97～0. 98,属于准铝质钙碱性岩石系列。岩石相对富集Rb、Th、U等大离子亲石元素,亏损Nb、Ta、Ti、P等高场强元素及Ba、Sr等部分大离子亲石元素。稀土元素配分曲线呈右倾型,轻稀土元素分馏明显,重稀土元素分馏较弱,且相对富集轻稀土元素,亏损重稀土元素,显示明显的负Eu异常(δEu=0. 36～0. 43)。锆石Hf同位素ε_(Hf)(t)比值为+6. 6～+9. 6,二阶段模式年龄T_(DM2)为760～950 Ma。综合岩石地球化学及同位素的研究表明,锡铁山花岗斑岩为高分异的I型花岗岩,岩浆源区主要为起源亏损地幔的新元古代新生地壳物质的部分熔融。结合区域构造背景和前人研究成果,认为本文锡铁山花岗斑岩形成于柴达木地块与祁连地块碰撞后伸展的大地构造环境。     

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.     

Composition, age, and origin of the ~620?Ma Humr Akarim and Humrat Mukbid A-type granites: no evidence for pre-Neoproterozoic basement in the Eastern Desert, Egypt

The Humr Akarim and Humrat Mukbid plutons, in the central Eastern Desert of Egypt, are late Neoproterozoic post-collisional alkaline A-type granites. Humr Akarim and Humrat Mukbid plutonic rocks consist of subsolvus alkali granites and a subordinate roof facies of albite granite, which hosts greisen and Sn–Mo-mineralized quartz veins; textural and field evidence strongly suggest the presence of late magmatic F-rich fluids. The granites are Si-alkali rich, Mg–Ca–Ti poor with high Rb/Sr (20–123), and low K/Rb (27–65). They are enriched in high field strength elements (e.g., Nb, Ta, Zr, Y, U, Th) and heavy rare earth elements (La _n /Yb _n ?=?0.27–0.95) and exhibit significant tetrad effects in REE patterns. These geochemical attributes indicate that granite trace element distribution was controlled by crystal fractionation as well as interaction with fluorine-rich magmatic fluids. U–Pb SHRIMP zircon dating indicates an age of ~630–620?Ma but with abundant evidence that zircons were affected by late corrosive fluids (e.g., discordance, high common Pb). εNd at 620?Ma ranges from +3.4 to +6.8 (mean?=?+5.0) for Humr Akarim granitic rocks and from +4.8 to +7.5 (mean?=?+5.8) for Humrat Mukbid granitic rocks. Some slightly older zircons (~740?Ma, 703?Ma) may have been inherited from older granites in the region. Our U–Pb zircon data and Nd isotope results indicate a juvenile magma source of Neoproterozoic age like that responsible for forming most other ANS crust and refute previous conclusions that pre-Neoproterozoic continental crust was involved in the generation of the studied granites.     

Zr/Hf ratio as an indicator of fractionation of rare-metal granites by the example of the Kukulbei complex,eastern Transbaikalia

The concept of granitic melt fractionation as the main process in the concentration of rare elements in granites calls for the development of a reliable method to determine the evolutionary sequences of granite series. We propose to use for this purpose a zirconium-hafnium indicator, the Zr/Hf weight ratio in granitic rocks (Zaraisky et al., 1999, 2000). By the example of three classic regions of rare-metal deposits, eastern Transbaikalia, central Kazakhstan, and Erzgebirge (Czech Republic and Germany), it was empirically shown that the Zr/Hf ratio of granites decreases during the fractional crystallization of granite magmas in the sequence granodiorite → biotite granite → leucogranite → lithium-fluorine granite. The reason is the higher affinity of Hf compared with Zr to a granite melt. This implies that the crystallization and settling of accessory zircon will cause the progressive enrichment of Hf relative to Zr in the residual melt. As a result, the Zr/Hf ratio decreases regularly in the series of sequential phases of granite intrusion related to a single magma chamber from granodiorite to biotite granite, leucogranite, and Li-F granite (from 45-30 to 10-2). Our experimental investigations supported the preferential enrichment of haplogranite melt in Hf and zircon crystals in equilibrium with melt in Zr (T= 800°C and P = 1 kbar). The Zr/Hf indicator was tested by the example of the wellknown Kukulbei rare-metal granite complex of eastern Transbaikalia (J3), which is unique in the degree of fractionation of initial granite melt with the formation of three phases of granite emplacement and vein derivatives. An important feature of the complex is its “short” differentiation trend. It was supposed that the granite magma of the first phase is parental, and the later phases forming small intrusive bodies in large massifs of biotite granites of the first phase are sequential products of its crystallization differentiation in a magma chamber. The biotite granites of the first phase are barren. The leucocratic granites of the second phase are accompanied by tin-tungsten greisen deposits (e.g., Spokoininskoe), and the upper part of cupola-like stocks of Li-F amazonite granites of the third phase host apogranite-type tantalum deposits (Orlovka, Etyka, and Achikan). In addition to three granite phases, the Kukulbei complex includes dikes of ongonites, elvans, amazonite granites, and chamber miarolitic pegmatites. All of the granitic rocks of the complex have similar isotopic ages of 142± 0.6 Ma. The Zr/Hf ratio decreases systematically from phase 1 (40–25), to phase 2 (20–10), and phase 3 (10–2). The ongonites, elvans, and pegmatites have similar Zr/Hf ratios (15-5), falling between the ranges of leucocratic muscovite granites and Li-F granites. Compared with other granite series, the granitic rocks of the Kukulbei complex show specific petrographic and geochemical features: they are strongly enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From the early to late intrusion phases, the degree of enrichment and depletion in these element groups increases regularly. This is accompanied by a significant decrease (from 40 to 2) in Zr/Hf, which can be used as a reliable indicator of genetic relations, degree of fractionation, and rare-metal potential of granites. Granites with Zr/Hf values lower than 25 are promising for prospecting for Sn, W, Mo, and Be greisen deposits, whereas the formation of Ta deposits requires Zr/Hf values lower than 10.     

Chemical Evolution of Zircons in the Paleogene Naegi Granite,Central Japan

The chemical composition of zircons from S‐ and I‐type ilmenite‐series granitic rocks in the Chubu district is summarized based upon recent electron probe microanalysis. Zircons in S‐type Busetsu granite of the Ryoke Metamorphic Belt have a homogeneous composition with minimum impurities, whereas those of I‐type Naegi granite in the non‐metamorphic Sanyo Belt are enriched in Hf, Y, REE, Th and U along the crystal rims. Similar enrichment has been observed in a variety of zircon called Naegite. These minor components are concentrated in the F‐rich fluid phase of residual melts of the Naegi granite magma, and are crystallized in pegmatites during the latest magmatic stage. High values of Nb and Ta in some Naegite reported previously are attributed to micro‐inclusion of fergusonite.     

小兴安岭东安金矿区细粒正长花岗岩U-Pb年龄、岩石地球化学、Hf同位素组成及地质意义

东安金矿区细粒正长花岗岩是小兴安岭燕山早期与吉黑东部斑岩型-矽卡岩型钼多金属矿床有关的花岗岩带组成岩体之一.为了解区域燕山早期岩浆演化和大规模钼多金属热液的成矿作用,进一步提升东安金矿成矿地质背景的研究程度,对该花岗岩进行了岩石地球化学、锆石U-Pb年龄和Hf同位素研究,讨论了岩石成因、岩浆源区和构造背景.获得细粒正长花岗岩锆石LA-ICP-MS U-Pb定年结果184±2 Ma,MSWD=1.2,为早侏罗世.岩石富硅和钾(K₂O/Na₂O值为1.46~1.81),低钙、镁和Mg#(Mg#=12.79~23.52),A/CNK=1.05~1.14,属高钾钙碱性、弱过铝质系列岩石.岩石富集大离子亲石元素(Rb、K)和不相容元素(Th、U),亏损高场强不相容元素(Nb、Ti等),轻、重稀土元素分馏强烈,轻微负Eu异常(Eu/Eu*=0.76~0.92).综合岩石地球化学特征、Harker图解、Ce-SiO₂和(K₂O+Na₂O)/CaO-(Zr+Nb+Ce+Y)判别图解确定岩石为高分异I型花岗岩.锆石的176Hf /177Hf值为0.282 588~0.282 775,ε_Hf(t)值为-2.35~+3.94,二阶段模式年龄T_DM2为973~1 386 Ma,岩浆源区应主要为起源于亏损地幔的中新元古代新增生陆壳的部分熔融,有硅铝质地壳物质的加入.研究表明,岩石形成于古太平洋板块俯冲引起大陆弧后伸展和岩石圈减薄的构造背景,幔源岩浆底侵为地壳熔融提供了热动力.燕山早期伸展体制下大陆岩浆弧环境的中-浅成、高钾钙碱性花岗质小侵入体是吉黑东部斑岩型-矽卡岩型钼多金属矿床找矿的主要目标.