四川雪宝顶W-Sn-Be矿床中矿物化学组成及矿床成因

雪宝顶矿床位于四川省的松潘甘孜造山带中,以出产大颗粒含W-Sn-Be-F-P的矿物而闻名,前人对该矿床已经开展了大量的研究,但缺乏对粗粒矿物的主次痕量元素研究。本次研究采用X射线荧光光谱(XRF)、电子探针(EMPA)和电感耦合等离子体质谱(ICP-MS)技术对矿床中各矿物的主次痕量元素进行测试分析。结果显示,雪宝顶矿床中的绿柱石、白钨矿、锡石、白云母、萤石、磷灰石、电气石,除富含W、Sn、Be、Na、K、Ca等主要成矿元素外,还富集Li、Rb、Cs等碱金属元素和F、B、P等挥发份。其中,雪宝顶绿柱石中富含Li(3484~4243μg/g)、Rb(39.3~71.1μg/g)、Cs(2955~3526μg/g);白云母中Li、Rb和Cs元素含量分别高达4243μg/g、72.3μg/g和3526μg/g;磷灰石中除主量元素P外,F(4.48%~5.21%)含量相对较高;电气石中的B含量高达30990~32880μg/g。雪宝顶矿床中的花岗岩岩体W、Sn、Be、Li、Rb、Cs、F、B、P等元素相对富集,但CaO含量(0.46%~0.82%)相对较低。其中Li、F、B、P等元素对成矿元素在成矿流体内的富集起到了极大的促进作用。矿区内大理岩是一种富Ca的方解石大理岩,为成矿提供了大量的Ca元素,有利于粗粒矿物的大规模沉淀。因此,粗粒矿物中的W、Sn、Be、Li、Rb、Cs、F、B、P等元素主要来源于原始岩浆流体,大理岩地层为粗粒矿物提供了大量的Ca元素。     

川西北雪宝顶钨锡铍矿床的成矿年代及其构造示踪意义

研究表明,川西北雪宝顶矿床的白云母40Ar/39Ar坪年龄为(189.9±1.8)Ma,说明雪宝顶矿床形成于印支晚期—燕山早期,是三叠纪华北板块与扬子板块碰撞的产物。文章通过雪宝顶矿床与甲基卡、可尔因和丹巴等伟晶岩型矿床的时空位置对比,并依据伟晶岩对大陆活动的示踪作用,推测中生代松潘-甘孜造山带的演化过程为:华北陆块、羌塘-昌都陆块分别与扬子陆块碰撞后,构造应力自北向南、自西向东逐步向松潘-甘孜地块的中心传递,雪宝顶、甲基卡、可尔因地区相继进入相对稳定发展阶段,构造应力最后在丹巴地区汇聚,形成丹巴白云母矿床。     

板状绿柱石晶体的结构测定

自然界中绿柱石晶体多为柱状,具板状晶形的绿柱石非常少见。本文对产于四川雪宝顶云英岩晶洞中的无色透明板状绿柱石进行了精确的结构分析,并与产于阿尔泰山号伟晶岩脉中的柱状绿柱石进行了比较。与阿尔泰柱状绿柱石相比,雪面板状绿石富Ｌi、Ｎａ,ｃ／ａ值较高,为１．００１,属钠－锂绿柱石或“四面体”绿柱石。本文还对这种特殊形貌柱石的形成机制进行了初步讨论,成矿流体中Ｌi的浓度以及Ｓi的化学形态可能是影响柱石忻驳闹     

四川雪宝顶W-Sn-Be矿床矿物学特征和形成机制

四川雪宝顶W-Sn-Be矿床位于龙门山西北缘,主要赋存在盘口和浦口岭花岗岩之间的大理岩张性裂隙中。雪宝顶矿床中出现的矿物晶体颗粒巨大,且矿脉中矿物分带明显。矿脉在花岗岩中主要由绿柱石、锡石、白云母和钾长石(fd1、fd2和fd3)组成,在大理岩围岩中则由绿柱石、白钨矿、锡石、萤石、方解石、石英、钠长石晶体(Ab4和Ab5)以及针状电气石和细粒磷灰石组成。3种不同形态的钾长石和2种不同形态的钠长石贯穿了整个矿脉的演化。随着围岩从花岗岩到大理岩的转换,晶体颗粒从小于1 cm的绿柱石、锡石演化至可达20 cm的绿柱石、锡石、萤石和白钨矿。采用EPMA、XRF、ICP-MS对单矿物颗粒进行全岩测试分析,结果显示:雪宝顶板状绿柱石介于Na-Li绿柱石和Li-Cs绿柱石之间,白钨矿中富集∑REE+Y(350×10~(-6)),白云母属于含Li白云母,磷灰石属于氟磷灰石,钾长石和钠长石比较纯净[fd1(Or 95.34~93.96)、fd2(Or 96.28~97.88)、fd3(Or 95.74~98.39)、Ab4(Ab 99.19~100)、Ab5(Ab 99.58~100)]。结合前人研究资料推测矿床形成机制为:在花岗岩演化的晚期,富F流体的脱熔作用大量富集了Li、Rb、Cs、W、Sn、Be、P等元素。这些来自于熔体的元素以不同的化合物形式(如SnF)在分离结晶过程中富集,通过成矿流体运移然后在花岗岩裂隙中小规模沉淀。花岗岩体的冷却引发的体积缩小导致了大理岩围岩中出现了放射状的张性裂隙。张性裂隙是控制成矿流体输运的主要通道,并引发了流体不混溶(相分离)。这个过程还伴随着包裹体均一温度不断下降和含矿络合物与围岩之间不断发生反应导致络合物不断分解。此时,成矿围岩从花岗岩变成大理岩,含F络合物大量被破坏造成成矿物质W-Sn-Be等元素大量沉淀,形成颗粒巨大的矿物晶体。选取与大颗粒绿柱石晶体共生的云母样品进行Ar-Ar定年并获得反等时线年龄195.7±2.5 Ma,代表了雪宝顶矿床形成的主成矿期年龄。     

Genesis of the Xuebaoding W–Sn–Be Crystal Deposits in Southwest China: Evidence from Fluid Inclusions,Stable Isotopes and Ore Elements

The Xuebaoding crystal deposit, located in northern Longmenshan, Sichuan Province, China, is well known for producing coarse‐grained crystals of scheelite, beryl, cassiterite, fluorite and other minerals. The orebody occurs between the Pankou and Pukouling granites, and a typical ore vein is divided into three parts: muscovite and beryl within granite (Part I); beryl, cassiterite and muscovite in the host transition from granite to marble (Part II); and the main mineralization part, an assemblage of beryl, cassiterite, scheelite, fluorite, apatite and needle‐like tourmaline within marble (Part III). No evidence of crosscutting or overlapping of these ore veins by others suggests that the orebody was formed by single fluid activity. The contents of Be, W, Sn, Li, Cs, Rb, B, and F in the Pankou and Pukouling granites are similar to those of the granites that host Nanling W–Sn deposits. The calculated isotopic compositions of beryl, scheelite and cassiterite (δD, ?69.3‰ to ?107.2‰ and δ¹⁸O_H2O, 8.2‰ to 15.0‰) indicate that the ore‐forming fluids were mainly composed of magmatic water with minor meteoric water and CO₂ derived from decarbonation of marble. Primary fluid inclusions are CO₂? CH₄+ H₂O ± CO₂ (vapor), with or without clathrates and halites. We estimate the fluid trapping condition at T = 220 to 360°C and P > 0.9 kbar. Fluid inclusions are rich in H₂O, F^‐ and Cl^‐. Evidence for fluid‐phase immiscibility during mineralization includes variable L/V ratios in the inclusions and inclusions containing different phase proportions. Fluid immiscibility may have been induced by the pressure released by extension joints, thereby facilitating the mineralization found in Part III. Based on the geochemical data, geological occurrence, and fluid inclusion studies, we hypothesize that the coarse‐grained crystals were formed by: (i) the high content of ore elements and volatile elements such as F in ore‐forming fluids; (ii) occurrence of fluid immiscibility and Ca‐bearing minerals after wall rock transition from granite to marble making the ore elements deposit completely; (iii) pure host marble as host rock without impure elements such as Fe; and (iv) sufficient space in ore veins to allow growth.     

40Ar/39Ar Dating of Xuebaoding Granite in the Songpan-Garzê Orogenic Belt, Southwest China, and its Geological Significance

<正>Thus far,our understanding of the emplacement of Xuebaoding granite and the occurrence and evolution of the Songpan-Garze Orogenic Belt has been complicated by differing age spectra results.Therefore,in this study,the ~(40)Ar/~(39)Ar and sensitive high resolution ion micro-probe(SHRIMP) U-Pb dating methods were both used and the results compared,particularly with respect to dating data for Pankou and Pukouling granites from Xuebaoding,to establish ages that are close to the real emplacements.The results of SHRIMP U-Pb dating for zircon showed a high amount of U,but a very low value for Th/U.The high U amount,coupled with characteristics of inclusions in zircons,indicates that Xuebaoding granites are not suitable for U-Pb dating.Therefore,muscovite in the same granite samples was selected for ~(40)Ar/~(39)Ar dating.The ~(40)Ar/~(39)Ar age spectrum obtained on bulk muscovite from Pukouling granite in the Xuebaoding,gave a plateau age of 200.1±1.2 Ma and an inverse isochron age of 200.6±1.2 Ma.The ~(40)Ar/~(39)Ar age spectrum obtained on bulk muscovite from Pankou granite in the Xuebaoding gave another plateau age of 193.4±1.1 Ma and an inverse isochron age of 193.7±1.1 Ma. The ~(40)Ar/~(36)Ar intercept of 277.0±23.4(2σ) was very close to the air ratio,indicating that no apparent excess argon contamination was present.These age dating spectra indicate that both granites were emplaced at 200.6±1.3 Ma and 193.7±1.1 Ma,respectively.Through comparison of both dating methods and their results,we can conclude that it is feasible that the muscovite in the granite bearing high U could be used for ~(40)Ar/~(39)Ar dating without extra Ar.Based on this evidence,as well as the geological characteristics of the Xuebaoding W-Sn-Be deposit and petrology of granites,it can be concluded that the material origin of the Xuebaoding W-Sn-Be deposit might partially originate from the Xuebaoding granite group emplacement at about 200 Ma.Moreover,compared with other granites and deposits distributed in various positions in the Songpan-Garze Orogenic Belt,the Xuebaoding emplacement ages further show that the main rare metal deposits and granites in peripheral regions occurred earlier than those in the inner Songpan-Garze.Therefore,~(40)Ar/~(39)Ar dating of Xuebaoding granite will lay a solid foundation for studying the occurrence and evolution of granite and rare earth element deposits in the Songpan-Garze Orogenic Belt.     

雪宝顶绿柱石的谱学研究

本文对雪宝顶绿柱石的晶体化学、矿物谱学、热释光和流体包裹体特征等进行了分析讨论。结果表明,雪宝顶绿柱石化学成分具有富碱、富水、过渡金属离子以Ｆｅ＾３＋、Ｆｅ＾２＋为主的特点。碱金属离子,水和Ｆ＾２＋存在于绿柱石结构隧道中,隧道水分为Ⅰ型和Ⅱ型两类,Ⅰ型水可以进一步区分为Ⅰ１和Ⅰ２两亚类,Ｆｅ＾２＋主要与隧道水结合形成水合离子「Ｆｅ＾２＋（Ｈ２Ｏ）」。Ｆｅ＾３＋主要占位于绿柱石ＡｌＯ６八面体中的Ａｌ     

四川雪宝顶钨锡铍矿床流体包裹体研究及其意义

四川雪宝顶钨锡铍矿床产于花岗岩体与三叠系地层大理岩的接触带,赋矿石英脉受大理岩中的劈理破碎带控制。绿柱石与白钨矿中的包裹体可分为熔融包裹体、流体熔融包裹体和流体包裹体3类。流体包裹体又可分为H2O包裹体、CO2包裹体和CO2-H2O包裹体,其中,绿柱石中以富含CO2-H2O包裹体为显著特征。加热时,富H2O相CO2-H2O包裹体完全均一至H2O相,富CO2相CO2-H2O包裹体完全均一至CO2相,而二者的完全均一温度和均一压力一致,表明它们是同期捕获的CO2-低盐水不混溶包裹体组合。与绿柱石相比,白钨矿中CO2-H2O包裹体数量明显减少,H2O包裹体数量增多,成矿压力与成矿温度均有所降低。含CO2流体在花岗岩体与大理岩接触带附近发生流体不混溶和相分离,CO2的出溶使成矿流体中pH值升高,f(O2)降低,导致钨的溶解度降低而沉淀,这是形成白钨矿的主要原因。