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作者简介:

陆蕾,女,1987年生。博士,主要从事稀土等战略矿产的调查研究工作。E-mail:lulei0830@qq.com。

通讯作者:

王成辉,男,1983年生。副研究员,主要从事金矿和稀有稀散稀土矿产研究。E-mail:wangchenghui131@sina.com。

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目录contents

    摘要

    云南陇川龙安稀土矿是云南境内唯一开采的离子吸附型稀土(iREE)矿床,其成矿母岩为邦棍尖山花岗岩。近年来该花岗岩风化壳中相继发现了一系列iREE矿化点甚至矿床,其中不乏重稀土(HREE)矿。本文选取邦棍尖山南段的花岗岩进行岩石学、矿物学、地球化学和年代学等研究工作,并探讨其对iREE(甚至离子吸附型重稀土(iHREE))成矿的制约。邦棍尖山岩体的主要岩性为黑云母二长花岗岩,本研究测得花岗岩锆石U-Pb年龄为50.33 Ma(50.33±0.30 Ma,MSWD=0.15),形成于喜山期(古近纪),是目前发现的成矿母岩最年轻的iREE矿床。花岗岩具有以下地球化学特征:高硅高碱、低铁低镁,A/CNK>1.1,高钾-强过铝质,S型。岩体轻稀土(LREE)相对富集,轻重稀土分异较强烈(LREE/HREE为2.54~8.98),Eu负异常(δEu=0.06~0.17);微量元素显示出高Rb、Th,低Ba、Nb、Sr、Zr、Hf、Ti的特征,岩浆岩高度分异。邦棍尖山花岗岩中的(含)稀土矿物主要是榍石(∑REE=14506.24×10-6,LREE/HREE=1.14,n=6)、褐帘石(∑REE=232860.82×10-6,n=2)、褐钇铌矿和锆石,其次为少量独居石、磷钇矿、钍石、含稀土萤石和氟碳酸盐矿物等。此外,黑云母(∑REE=168.60×10-6,LREE/HREE=1.41,n=10)和斜长石(∑REE=123.60×10-6,LREE/HREE=2.77,n=8)中少量的REE对原岩也有贡献。(含)稀土矿物是基岩中REE含量的主要贡献者,这些矿物在自然风化作用下风化-解离后吸附于黏土矿物之上即有可能形成iREE矿床。通过本次研究得出以下认识:① 花岗岩的演化主要影响REE的迁移、分馏和再富集,与REE含量变化关系不大;② 花岗岩演化过程中产生的热液使REE从原矿物中迁出并形成新的(含)稀土矿物,是iREE(甚至iHREE)成矿的关键;③ 龙安iREE矿床基岩中,榍石、褐帘石、钍石、含稀土萤石和氟碳酸盐矿物是iREE成矿的主要来源,其次为斜长石和黑云母,这些矿物总体显示出LREE含量相对较高,从而使矿床LREE相对富集。

    Abstract

    The Long'an deposit is the only mining ion-adsorption type REE (iREE) deposit in Yunnan Province, the parent rock of which is the Banggunjianshan (BGJ) granite. Recently, comparable systems have been recognized in the south-middle part of weathering BGJ granite. What's more, some of these deposits are relatively heavy REE (HREE) enrichment. In order to investigate the controlling factors of iREE deposit, the south part of BGJ granite has been chosen to study the petrology, mineralogy, geochemistry and chronology. The host rock of BGJ granite is biotite monzogranite, zircon U-Pb date of which is 50.33 Ma (50.33±0.30 Ma, MSWD=0.15), indicating that it was formed in Paleogene. It's the youngest age of parent rock of discovered iREE deposits. BGJ granite with high A/CNK ratios (>1.1), are strongly potassium rich and display peraluminous characteristics similar to S-type granite. BGJ granite is relatively LREE enriched, has strongly fractionated REE patterns (LREE/HREE=2.54~8.98), moderately negative Eu anomalies (Eu/Eu*=0.06~0.17), is high in Rb, Th, and depleted in Ba, Nb, Sr, Zr, Hf, Ti. REE bearing minerals (REE minerals) are the key factor for REE concentration in the rock. The REE minerals in BGJ granite are sphene (∑REE=14506.24×10-6, LREE/HREE=1.14, n=6), allanite (∑REE=232860.82×10-6, n=2), fergusonite, zircon, thorite, fluorite, REE-fluocarbonate; however, apatite, monazite and xenotime are not uncommon. In addition, biotite (∑REE=168.60×10-6, LREE/HREE=1.41, n=10) and feldspar (∑REE=123.60×10-6, LREE/HREE=2.77, n=8) also contribute to REE concentration in the BGJ granite. The REE bearing minerals dissolve in the weathering crust and release REE that could be the source of iREE deposits. Through this study, the following conclusions are obtained: ① REE migrate, fractionate and re-enrich because of the evolution of granite with little change in REE content; ② During granite evolution, REE moved out from the original minerals, subsequently forming secondary REE minerals that are the key to forming iREE (even iHREE) deposits; ③ In bedrock rocks (BGJ granite) of the Long'an iREE deposit, sphene, allanite, thorite, fluorite and REE-fluocarbonate minerals are the main sources of iREE mineralization, followed by feldspar and biotite. These minerals show that relative LREE enrichment led to the formation of iLREE deposit.

  • 离子吸附型稀土(ion-adsorption-type REE,iREE)矿是我国重要的稀土资源,以规模大、易采冶、低成本,同时富含Eu、Tb、Dy等附加值极高且其他途径难以获得的中、重稀土而被受重视。科技和新能源领域对稀土(特别是中、重稀土)资源需求量的增加推动了全球稀土资源的勘探工作,并相继在老挝、缅甸、泰国等东南亚一带,马达加斯加、马维拉、澳大利亚和巴西等热带、亚热带地区发现类似的iREE矿床,使我国的稀土资源优势地位受到挑战(Kanazawa et al.,2006; Sanematsu et al.,200920122013; Murakami et al.,2010; Fuyuno,2012; Simandl et al.,2014; 袁忠信等,2016; Mohamad et al.,2016; Padrones et al.,2017; 周美夫等,2020; 郑国栋等,2021)。

  • 云南iREE矿床主要分布于陇川—腾冲、临沧—勐海、建水—个旧—金平和元谋—牟定等地区,多显示出轻稀土(LREE)相对富集,个别地区(陇川—腾冲、临沧—勐海和元谋—牟定等)有重稀土(HREE)产出。陇川龙安iREE矿是云南境内最早发现且唯一仍在开采的iREE矿床,成矿母岩为邦棍尖山花岗岩,矿床位于岩体南段。近年来,邦棍尖山岩体中-南段也发现类似矿床,其中不乏富含重稀土(HREE)的矿化点甚至矿床(王登红等,20052013a2013b2017; Feng Wenjie et al.,2016; 陆蕾等,20192020; Lu Lei et al.,2020)。

  • 龙安iREE矿床自发现开采至今,对其成矿母岩甚至矿床的研究程度依旧很低。近年来邦棍尖山花岗岩风化壳中相继发现的矿化点和矿床说明该岩体具有形成iREE甚至iHREE矿床的成矿潜力。本文通过研究邦棍尖山南段花岗岩的岩石学、矿物学、地球化学和年代学等特征,旨在解决以下问题:① 查明邦棍尖山花岗岩的成岩时代及其与iREE成矿的关系; ② 揭示邦棍尖山花岗岩中的主要(含)稀土矿物及其对iREE成矿的制约; ③ 探讨花岗岩演化对iREE(特别是iHREE)成矿的影响。

  • 1 成矿地质背景

  • 1.1 矿区地质

  • 邦棍尖山花岗岩位于滇西南,属于特提斯-喜马拉雅成矿区,腾冲-陇川亚区,北东-南西向延展,呈长条带状岩基产出,与围岩中元古界高黎贡山群呈交代侵入接触; 宽约10 km,长约40 km,出露面积约3.95 km2; 夹持于大盈江断裂带与龙川江断裂带之间,受控于其中的邦东脆-韧性剪切带、芒东脆-韧性剪切带及河头脆-韧性剪切带; 其中未见褶皱构造(图1a; 云南省地矿局,1990)。岩体具有多期次、多旋回的特征,至少经历了三期岩浆岩作用,主要发育有似斑状中粗粒黑云角闪钾长-二长花岗岩和中细粒黑云母钾长-二长花岗岩。岩体岩性岩相分带明显,主要是似斑状粗粒黑云钾长花岗岩、斑状黑云二长花岗岩和细粒黑云二长花岗岩。岩体东西两侧出露中元古界高黎贡山群混合岩化片麻岩、黑云变粒岩等(图1b)。岩体中可见该变质岩的零星捕虏体。邦棍尖山岩体风化壳中发现的iREE矿床主要分布于岩体中—南部。

  • 矿区花岗岩风化壳富厚,厚度多>10 m,保存完整,由上而下可分为:表土层—全风化层—半风化层。表土层由腐植层和红土化层组成; 腐植层内含较多石英和微量长石(多已风化为高岭土),植物根茎发育,厚0~0.3 m; 红土化层呈为砖红色、红色、黄色砂质黏土,石英含量大约30%。平均厚2.13 m。全风化层厚度>15 m,长石绝大多数已高岭土化,约占60%,石英约30%; 黑云母铁染强烈,约5%~6%。半风化层成分与全风化层相似,长石风化程度减弱,高岭土化仅见于长石晶体边缘,黑云母、磁铁矿、黄铁矿增加。

  • 研究区位于云南高原南端,浅切割带状中山内的二、三级台地地貌区。海拔1000~1300 m,二级台地台面高1050~1100 m左右,三级台地台面高1300 m左右。西坡陡坡区坡脚约34°,东坡台面区坡脚约10°~25°。相对高差多在60~80 m,区内年均气温18.7℃。年均降雨量1515 mm,年降雨166 d,年均日照2316 h,占可照时数的53%(云南省地矿局,1990)。属南亚气候,植物繁茂,雨量充沛。岩石化学物理风化作用十分强烈,土壤生物作用活跃,形成大面积红壤。可见岩石风化壳厚度在20 m以上,风化壳大多保存完整,未见基岩出露,属全覆式风化壳。

  • 1.2 岩石学特征

  • 研究区所采样品主要是黑云母二长花岗岩,球状风化,致密块状(图2a、b),出露于其风化剖面附近(图2c)。显微镜下观察,可将所采样品分为:似斑状中粗粒黑云角闪二长花岗岩(bgj1-j1)和中细粒黑云母二长花岗岩(bgj1-j2、bgj3-j1)。现将两种岩石类型分述如下:

  • 似斑状中粗粒黑云角闪二长花岗岩(bgj1-j1):似斑状、中粗粒结构,块状构造。岩石斑晶主要是钾长石,含量约10%~15%,自形—半自形板柱状,粒径约1~2.5 cm; 基质粒径0.1~1 mm,基质显晶质结构。造岩矿物由长石、石英和黑云母组成,其次为少量角闪石; 条纹-微斜长石40%~45%,粒度0.5~5 mm,半自形板柱状,条纹状、格子状双晶发育,高岭土化(图2d、e); 中长石15%~20%,粒度0.5~3 mm,半自形板柱状—他形,聚片双晶发育; 石英22%~28%,粒度0.5~3.5 mm,他形粒状,波状消光; 黑云母5%~15%,片状结构,粒径0.5~2 mm; 角闪石1%~2%,半自形柱状—他形,浅黄绿色—浅褐色,黑云母化,黑云母呈片状沿角闪石解理交代(图2d)。副矿物主要是磁铁矿、钛铁矿、榍石、磷灰石和锆石等(图2f); 其中,钛铁矿<1%,多呈半自形板柱状与暗色矿物共生; 榍石≤1%,自形—半自形粒状,d=0.01~1 mm,个别达2 mm。

  • 图1 滇西地区花岗岩分布简图(a)和邦棍尖山花岗岩地质简图(b)

  • Fig.1 Geological map of west Yunnan granite (a) and geological sketch (b) of the Banggunjianshan granite, Yunnan Province

  • 1 —中元古代片麻状花岗闪长岩; 2—中生代正长岩; 3—中生代中粗粒二长花岗岩; 4—中生代似斑状中—细粒黑云母钾长花岗岩岩; 5—中生代似斑状粗粒黑云钾长花岗岩; 6—中生代细粒黑云母花岗; 7—古近纪辉长岩; 8—元古代高黎贡山变质岩; 9—新近系砂砾岩、砂岩; 10—第四系砂、砾、粗土质砂; 11—断层; 12—iREE矿区; 13—采样位置

  • 1 —Mesoproterozoic gneissic granodiorite; 2—Mesozoic syenite; 3—Mesozoic coarse grain monzonitie; 4—Mesozoic porphyroid fine grain biotite moyite; 5—Mesozoic porphyroid coarse grain biotite-feldspar granite; 6—Mesozoic fine grain biotite granite; 7—Paleogene gabbro; 8—Proterozoic Era Gaoligong metamorphic rocks; 9—Neogene sandstone; 10—Quaternary sandstone; 11—fault; 12—iREE deposit; 13—sampling location

  • 中细粒黑云母二长花岗岩(bgj1-j2、bgj3-j1):中细粒结构,块状构造。等粒花岗结构,粒径0.3~2.5 mm。造岩矿物主要由长石、石英和黑云母组成(图2g、h、e); 长石主要是钾长石,条纹-微斜长石居多,半自形板柱状,条纹状、格子状双晶发育,轻微高岭土化(图2h),粒径0.5~2.5 mm,含量约35%~40%; 中长石半自形板柱状—他形,聚片双晶发育,钾长石化,粒度0.5~2 mm,含量15%~25%; 石英他形粒状,波状消光,粒度0.5~3.5 mm,含量20%~25%; 黑云母半自形片状,浅褐色—深棕色,粒径约0.3~1 mm,含量5%~9%,轻微白云母化,铁泥质化。副矿物主要是钛铁矿、榍石、磷灰石和锆石等,含量1%~1.5%,零星分布(图2i)。

  • 2 样品和测试方法

  • 2.1 样品

  • 实验样品采自邦棍尖山花岗岩体中—南段,该区花岗岩风化层富厚,因人工挖掘露出新鲜的风化壳剖面甚至底部新鲜花岗岩,采样位置见图1b和图2a~c。该区出露两种类型花岗岩,中细粒黑云母二长花岗岩和中粗粒黑云母二长花岗岩,二者出露位置距离约4~5 m,接触界面不清晰。根据野外肉眼判断选取不同粒度的花岗岩进行采样工作,并对其上覆风化壳进行了野外稀土沉淀快速分析实验,确认该区风化壳中含较富的离子型稀土,随后对各风化层分层采样。中细粒黑云二长花岗采样2件,采样点海拔1571 m,上覆风化壳样品野外稀土快速滴定实验结果较弱,岩石编号bgj1-j1和bgj1-j2; 中粗粒似斑状黑云二长花岗岩上覆风化壳样品野外滴定实验结果较好,白色沉淀显著,采样点海拔1057 m,编号bgj3-j1。

  • 图2 云南邦棍尖山花岗岩(a、b)及其风化剖面(c)照片和花岗岩显微镜下(单偏光d; 正交偏光e~i)照片

  • Fig.2 Photo and microscope picture (single polarized light d; crossed polarized light e~i) of the Banggunjianshan granite (a, b) and weathering profile (c) , Yunnan Province

  • Qtz—石英; Kfs—钾长石; Mc—微斜长石; Pl—斜长石; Bt—黑云母; Amp—角闪石; Sph—榍石; Ap—磷灰石; Zrn—锆石

  • Qtz—quartz; Kfs—K-feldspar; Mc—microcline; Pl—plagioclase; Bt—biotite; Amp—amphibole; Sph—sphene; Ap—apatite; Zrn—zircon

  • 2.2 测试方法

  • 岩石样品首先磨制成薄片,利用偏光显微镜(型号:Eclipse LV100POL Stand(100~240 V))镜下详细观察并对目标区域和典型矿物进行圈定和拍照,并通过能谱和电子探针进一步对比查证。研究选取bgj1-j2岩石样品进行锆石U-Pb同位素测年工作。锆石样品处理按照指定粒度粉碎,清洗、烘干和筛选,然后采用磁选和重液分离技术将锆石从矿物中选出,再经双目镜下人工提纯,挑选出晶型较为完整且粒度较大无明显裂隙和包裹体的锆石。随后进行制靶并进行锆石阴极发光(CL)高清图像采集,以观察内部结构。部分样品破碎至200目,烘干后进行岩石的主量、微量和稀土元素的测试分析工作。

  • 花岗岩中稀土矿物的电子探针分析和LA-ICP-MS矿物原位分析在自然资源部成矿作用与资源评价重点实验室完成。电子探针分析采用JXA-8230电子探针分析仪和X-max能谱仪,测试条件为加速电压15 kV或20 kV,激发电流20 nA,电子束直径为5 μm。LA-ICP-MS矿物原位分析采用ASI J-200 343 nm飞秒激光(Applied Spectra公司,美国)和X-Series电感耦合等离子体质谱仪(Thermo Fisher公司,德国)联机系统上进行。采用点方式剥蚀样品,束斑直径50 μm,激光频率10 Hz,能量密度约5 H/cm2,剥蚀坑深度20~30 μm,以He气作为运移样品剥蚀颗粒的载气,样品信号采集时间20 s,之前采集30 s空白。

  • 锆石U-Pb同位素定年在自然资源部成矿作用与资源评价重点实验室利用LA-ICP-MS分析完成。详细的仪器参数和分析流程见Zong Keqiang et al.(2017)。GeolasPro激光剥蚀系统由COMPexPro 102 ArF193 nm准分子激光器和MicroLas光学系统组成,ICP-MS型号为Agilent 7700e。本次分析的激光束斑和频率分别为36 μm和10 Hz。每个时间分辨分析数据包括大约20~30 s空白信号和50 s样品信号。

  • 花岗岩样品的主、微量及稀土元素分析测试在国家地质实验测试中心完成,主量元素测试方法为X荧光光谱法(XRF); 微量和稀土元素测试方法为电感耦合等离子质谱法(ICP-MS),实验仪器为X-Series型电感耦合等离子质谱仪(美国Thermo公司),分析误差小于5%。

  • 3 结果

  • 3.1 年代学特征

  • 邦棍尖山黑云二长花岗岩中,锆石颗粒自形程度高,半自形—自形短柱状,少数长柱状,长50~200 μm,长宽比1∶1~3∶1。阴极发光图像中,锆石振荡环带发育明显(图3a)。锆石的U含量384.3×10-6~2344.8×10-6,Th含量244.0×10-6~2521.2×10-6,Th/U比值0.31~1.81,均大于0.1,为典型的岩浆锆石特征,在测试过程中,选择锆石边部环带打点,一共测25个分析点进行加权年龄分析。

  • 锆石206Pb/238U年龄为50.33±0.30 Ma(n=25,MSWD=0.15),在锆石U-Pb年龄谐和图上分析点均分布在谐和线上,显示良好的谐和性,表明锆石形成后处于封闭体系,无明显U或者Pb的加入和带出,因此该年龄结果代表了岩浆岩的就位时代(图3b)。

  • 3.2 邦棍尖山花岗岩地球化学特征

  • 邦棍尖山花岗岩的主量元素列于表2。SiO2含量69.89%~75.37%,K2O含量4.99%~5.84%,Na2O含量2.32%~2.98%,TFeO含量1.14%~3.8%,MgO含量0.10%~0.78%,具高硅、碱,低铁、镁的特征。在岩浆岩TAS图解中,岩石均落入花岗岩区域; 但样品bgj1-j1中TiO2、TFeO、MgO、CaO的含量相对于bgj1-j2、bgj3-j1含量较高,岩性偏向花岗闪长质(图4)。

  • 表1 云南邦棍尖山花岗岩(bgj1-j2,n=25)锆石LA-ICP-MS U-Pb定年结果

  • Table1 LA-ICP-MS zircon U-Pb analytical data of the Banggunjianshan granite (bgj1-j2, n=25) , Yunnan Province

  • 邦棍尖山花岗岩的地球化学分布变化具有一定规律性:随着SiO2含量的升高,FeO、MgO、TiO2、MnO、CaO和P2O5含量逐渐降低,体现出其成分与源区的较大区别(图5)。花岗岩的分异指数DI为48.83~92.51,CIPW刚玉指数0~4.1,K2O+Na2O含量7.31%~8.61%,K2O/Na2O比值为1.16~2.15; 碱度系数(K2O+Na2O)/Al2O3=0.49~0.63,钠质系数Na2O/(K2O+Na2O)=0.31~0.46,铁氧化度Fe2O3/(Fe2O3+FeO)=0.10~0.31,铝饱和指数A/CNK=1.25~1.57。岩浆分异演化表现为SiO2、Na2O与K2O、CaO、FeO、MgO、TiO2的分离,随着分异指数的增加,SiO2、Na2O增加,而FeO、MgO、CaO、K2O的逐渐减少。样品K2O/Na2O>1,A/CNK>1.1,在K2O-SiO2和Na2O-K2O图解中,样品几乎都投入高钾钙碱性系列区域,整体显示出高钾-强过铝质钙碱性花岗岩的特征(图6)。

  • 图3 云南邦棍尖山黑云二长花岗岩代表性锆石颗粒阴极发光照片(a)和LA-ICP-MS锆石U-Pb加权年龄图(b)

  • Fig.3 Cathodoluminescence (CL) images of representative zircon grains (a) and LA-ICP-MS zircon U-Pb weighted age diagram (b) for the Banggunjianshan granite, Yunnan Province

  • 图4 云南邦棍尖山花岗岩TAS分类图解(据Middlemost,1994

  • Fig.4 TAS diagram for classification of the Banggunjianshan granite, Yunnan Province (after Middlemost, 1994)

  • ∑REE含量209.31×10-6~809.59×10-6,LREE/HREE 2.54~8.98,LREE相对富集,轻重稀土分异较好; 岩石显示中度Eu亏损,δEu值随着岩浆岩的酸度增强而呈降低的趋势(0.17→0.06); Ce显示正异常,δCe为1.57~3.11,随着SiO2的增加,Ce呈现出轻微的负异常(图7a)。微量元素显示出高Rb、Th,低Ba、Nb、Sr、Zr、Hf、Ti的特征(图7b)。

  • 3.3(含)稀土矿物特征

  • 邦棍尖山花岗岩中的(含)稀土矿物主要是榍石、锆石、褐钇铌矿、褐帘石和钍石,其次为少量独居石、磷灰石、萤石(-Y)和含稀土氟碳酸盐矿物等(图8a),花岗岩中的主要稀土矿物的元素含量特征列于表2和图9a、b。其中,榍石在样品bgj1-j1中大量出现; 在样品bgj1-j2和bgj3-j1中含量减少至几乎不见,并出现了除磷灰石和锆石以外的其他(含)稀土矿物。本次研究中,斜长石、黑云母、榍石和褐帘石数据来自LA-ICP-MS矿物原位分析,其他矿物数据主要来自能谱电子探针测试。测试结果显示,除了副矿物,黑云母(∑REE=168.60×10-6,LREE/HRRE=1.41,n=10)和斜长石(∑REE=123.60×10-6,LREE/HREE=2.77,n=9)中含有少量REE(图8b),且黑云母与其母岩具有相似的稀土配分特征(图9b)。现将花岗岩中主要的(含)稀土矿物分述如下:

  • 榍石在样品bgj1-j1中含量较高(≥1%),而在样品bgj1-j2和bgj3-j1中的含量明显减少。显微镜下,榍石呈自形—半自形粒柱状。在样品bgj1-j1中,粒径较大,0.1~15 mm; 而样品bgj1-j2和bgj3-j1中,粒径约0.1~0.2 mm。这些榍石多呈独立矿物分布于石英和长石等矿物中,其REE含量∑REE=14506.24×10-6n=6; 图8a),约占矿物元素总含量的2.34%,轻重稀土含量较为均一,LREE/HREE比值1.14(图8a,图9b)。

  • 图5 云南邦棍尖山花岗岩主量元素哈克图(a~f)

  • Fig.5 Harker diagrams for the major element (a~f) of the Banggunjianshan granite, Yunnan Province

  • 图6 云南邦棍尖山花岗岩地球化学判别图(a~c)

  • Fig.6 Geochemical discrimination diagrams (a~c) for the Banggunjianshan granite, Yunnan Province

  • 图7 云南邦棍尖山花岗岩球粒陨石标准化稀土元素配分曲线(a)和原始地幔标准化微量元素蛛网图(b)

  • Fig.7 Chondrite-normalized REE patterns (a) and primitive mantle-normalized trace element patterns (b) for the Banggunjianshan granite, Yunnan Province

  • 褐帘石多呈他形粒状沿长石和云母的矿物边缘分布,在样品bgj1-j1中含量较低,在样品bgj1-j2和bgj3-j1中的含量增加。矿物粒度0.01~0.1 mm,其REE含量可达232860.82×10-6n=2; 图8b),约占总矿物的20.60%,LREE/HREE比值为36.14,显示出LREE相对富集(图8b,图9b)。

  • 表2 云南邦棍尖山花岗岩及其中主要稀土载体矿物的主量(%)、微量(×10-6)和稀土(×10-6)元素含量

  • Table2 Major (%) , trace elements (×10-6) and rare earth elements (×10-6) of the Banggunjianshan granite and REE bearing minerals, Yunnan Province

  • 注:“-”代表无此项数据。

  • 钍石多呈他形粒状,粒径约0.01~0.05 mm,可分为两种类型:① 呈独立矿物零星分布于云母、长石等矿物中,粒状,REE含量约13.04%(n=9),LREE/HREE比值为0.11(图8c、d); ② 呈他形粒状沿矿物晶纹或裂隙充填,F约占2.81%(n=3),与锆石、萤石和磷钇矿等矿物共生,REE含量约26.76%(n=3),LREE/HREE比值为0.33,LREE含量明显增加(图8c、e、f,图10)。

  • 图8 云南邦棍尖山花岗岩中稀土矿物的背散射图像(a~i)

  • Fig.8 BSE image of rare earth element minerals (a~i) in the Banggunjianshan granite, Yunnan Province

  • Spn—榍石; Mnz—独居石; Xtm—磷钇矿; Zrn—锆石; Trt—钍石; Fer—褐钇铌矿; Aln—褐帘石; Fl-REE—含稀土氟碳酸盐

  • Spn—sphene; Mnz—monazite; Xtm—xenotime; Zrn—zircon; Trt—thorite; Fer—fergusonite; Aln—allanite; Fl-REE—REE bearing

  • 图9 云南邦棍尖山花岗岩中稀土矿物的REE分布特征(a)和球粒陨石标准化稀土元素配分曲线(b)

  • Fig.9 Distribution of REE (a) and chondrite-normalized REE patterns of REE-minerals (b) in the Banggunjianshan granite, Yunnan Province

  • 褐钇铌矿是除榍石外岩石中含量较多的稀土矿物,多呈半自形粒状、柱状分布于石英、长石和黑云母中,粒径0.01~0.5 mm,其REE(特别是Y)含量较高,REE占总矿物的47.20%(n=3),LREE/HREE比值为0.14,Y/REE比值为0.29(图8d、g,图10)。

  • 锆石在邦棍尖山花岗岩中呈自形—半自形粒状,粒度0.01~0.2 mm,零星分布于石英、长石和黑云母等造岩矿物中。根据锆石的晶型和分布特征,可分为两种类型:① 早期分异结晶形成的自形粒柱状的锆石,主要分布于石英、长石和云母等造岩矿物中(图8b); ② 晚期被热液交代的半自形粒状锆石,多与褐帘石、钍石等矿物共生(图8b、c,图10)。

  • 图10 云南邦棍尖山花岗岩中(含)稀土矿物 LREE-HREE的配分特征

  • Fig.10 Distribution of LREE-HREE of REE-minerals in Banggunjianshan granite, Yunnan Province

  • 独居石、磷钇矿和含稀土氟碳酸盐矿物等稀土矿物在邦棍尖山花岗岩中较为少见,粒度小于20 μm,零星分布,但这些矿物中的REE含量通常较高,如独居石中REE含量约占总矿物的48.5%(n=2; 图8h,图10)、含稀土氟碳酸盐矿物REE含量约41.53%(n=3)。在此次研究中,部分矿物因受可挥发分(如F-、Cl-)等的影响,其矿物元素组成有所改变,如岩石中化学成分与褐帘石相似的矿物,其中Ca含量仅为0.47%,而F含量达8.05%,REE含量可达23.62%(n=7)。这类矿物亦是岩石中REE的来源。

  • 4 讨论

  • 4.1 年代学特征与iREE成矿

  • 对比华南的iREE成矿母岩的年代学特征,华南成矿花岗岩的锆石U-Pb年龄主要集中于461~384 Ma、242~228 Ma和198~94 Ma,岩浆侵入时期从加里东期—印支期—燕山期都有分布(吴澄宇等,19901992; 王登红等,20052014; 赵芝等,2017)。而云南境内的岩浆岩锆石U-Pb年龄主要集中分布于240~208 Ma和80~52 Ma两个区间,与iREE成矿有关的花岗岩主要是临沧花岗岩基(252~199 Ma)和高黎贡山花岗岩群(79~50.6 Ma)等(陆蕾等,20192020; Lu Lei et al.,2020)。邦棍尖山花岗岩属于高黎贡山岩群,本文测得其锆石U-Pb年龄为50.33±0.30 Ma,与前人所测数据相符(50.8~48.0 Ma; 巫嘉德,2014),将iREE成矿母岩的最晚成岩时代从燕山期(白垩纪)推到了喜山期(古近纪)。说明iREE的形成不受岩体形成年代的制约,而主要与岩石特性有关。

  • 表3 云南邦棍尖山花岗岩中含稀土矿物中的稀土分布特征

  • Table3 REE geochemical characteristics of REE minerals from Banggunjianshan granite, Yunnan Province

  • 4.2 岩石的地球化学特征对iREE成矿的制约

  • 邦棍尖山花岗岩具有高硅、高碱和低铁、低镁的特征,岩浆岩高度分异,SiO2的含量与FeO、MgO、TiO2、MnO、CaO和P2O5含量呈反比,与华南花岗岩相似(黄典豪等,1988; 吴澄宇等,19891990; 黄典豪,1993; 赵芝等,20142017)。花岗岩类型为S型,为地壳熔融的产物。岩石石英玻璃包裹体测温始熔温度为760℃,均一温度820~860℃,岩体形成条件为深成相(云南省地矿局,1990)。岩石REE含量较高,轻重稀土分异强烈,LREE相对富集。在SiO2-REE判别图中,SiO2与REE的含量变化并无明显相关性(图11a); 但在δEu-REE判别图中,δEu与HREE呈明显的正相关(图11b); 说明岩浆的分异对REE总含量变化影响不大,而主要影响LREE和HREE的迁移、分馏和富集。而轻、重稀土的再迁移和富集并形成新的轻、重稀土矿物,才是形成iREE(甚至iHREE)的关键。

  • 4.3 岩石矿物学特征对iREE成矿的制约

  • 花岗岩的稀土配分类型通常由其中含稀土矿物的类型和含量所决定。邦棍尖山花岗岩中的(含)稀土矿物主要是榍石、褐帘石、锆石和褐钇铌矿,其次为少量的钍石、独居石、磷钇矿、萤石和含稀土氟碳酸盐矿物等; 此外,黑云母和斜长石也贡献了少量的稀土。斜长石、黑云母和榍石、褐帘石等矿物在岩石中含量相对较高,这些矿物显示LREE相对富集; 磷钇矿、锆石、钍石和褐钇铌矿等相对富集HREE,但在岩石中的含量甚少; 使得邦棍尖山花岗岩整体表现出LREE较富。

  • 花岗岩风化壳常继承了其母岩的稀土配分特征:LREE相对富集的岩石风化后形成LREE型矿床(iLREE),HREE相对富集的岩石风化后形成HREE型矿床(iHREE)。对比相似区域花岗岩风化壳及其南岭一带花岗岩风化壳中的iREE矿床,通常花岗岩中REE含量大于150×10-6即有成矿的潜力(赵芝等,20142017; 陆蕾等,20192020)。本次研究中,黑云角闪二长花岗岩(bgj1-j1)中REE含量391.17×10-6,其上覆风化壳中可交换的稀土含量较低; 而黑云母二长花岗岩(bgj1-j2(REE=265.39×10-6)、bgj3-j1(REE=706.82×10-6))上覆风化壳中含有较高含量的可交换态稀土,甚至达到矿化级别(≤500.91×10-6)。说明成矿母岩富REE,其上覆风化壳并不一定成矿。黑云角闪二长花岗岩中,暗色矿物含量相对较高,出现角闪石和大量榍石,主要的(含)稀土矿物为榍石、磷灰石、褐帘石和锆石等; 通常,榍石和角闪石的出现,是稀土矿物(除褐帘石外)富集的否定标志; 此阶段,稀土多呈分散状态分布于岩石中。而黑云母二长花岗岩中,角闪石几乎不见,榍石含量明显减少,褐帘石含量增加,并出现了钍石、磷钇矿、褐钇铌矿、萤石和含稀土氟碳酸盐矿物等含稀土矿物,(含)稀土矿物种类明显增加。由此说明,(含)稀土矿物对iREE成矿的影响较大。

  • (含)稀土矿物在自然风化作用下解离后,稀土元素呈离子态(REE3+)随土壤溶液或水流迁移并被吸附在黏土矿物之上,才有可能形成iREE矿床。独居石、磷钇矿、褐钇铌矿和锆石等矿物的化学键较强,在自然风化条件下较为稳定,难以解离,这类矿物常以重矿物的形式残留,难以对iREE成矿作出贡献; 而榍石、磷灰石和褐帘石等矿物的可解离程度中等,在自然风化作用下缓慢解离,释放REE3+; 萤石、含稀土氟碳酸盐矿物等在自然风化作用下较易被解离,是风壳中REE3+的首要来源(杨岳清等,1981; Bao Zhiwei et al.,2008; 赵芝等,2017)。

  • 邦棍尖山花岗岩中,褐帘石、钍石甚至锆石在不同类型/期次花岗岩中呈现出不同的结构特征,同时中—晚期岩石中常出现萤石、含稀土氟碳酸盐矿物等热液矿物,说明岩浆岩演化过程中产生的热液作用在REE的迁移和富集中起着重要作用。在酸性条件下,REE3+常常与热液中的F-、Cl-、CO32-等离子形成络合物迁移; 而HREE因具有相对于LREE较小的离子半径,更易于被迁移,在热液作用晚期沉淀富集,形成萤石、氟碳钙钇矿等一类重稀土矿物(Choppin et al.,197619831984; Wood et al.,1990)。热液作用下形成的(含)稀土矿物,其中HREE含量相对早期形成的矿物较高; 同时,其化学成分受热液作用影响,相对早期岩浆分离结晶的矿物更为复杂,化学键也相对较弱,这类矿物在自然风化作用下也更易被解离。

  • 图11 云南邦棍尖山花岗岩SiO2-REE和δEu-REE判别图

  • Fig.11 Diagrams of SiO2-REE and δEu-REE of the Banggunjianshan granite, Yunnan Province

  • 综上所述,邦棍尖山花岗岩中对iREE成矿有利的(含)稀土矿物主要是榍石、褐帘石、钍石、萤石和含稀土氟碳酸盐矿物等; 此外,斜长石和黑云母中少量的REE对矿床亦有贡献。由于花岗岩中的主要(含)稀土矿物相对富集LREE,而萤石和含稀土氟碳酸盐矿物等HREE较富的矿物在岩石中少见,使花岗岩风化壳中主要富集轻稀土离子,从而更有利于形成LREE型iREE矿床。在今后类似区域的找矿工作中,REE含量高(≥150×10-6)且为中—晚期花岗岩形成的风化壳,更有利于形成iHREE矿。

  • 5 结论

  • (1)黑云二长花岗岩是邦棍尖山花岗岩风化壳中iREE的成矿母岩。岩石中的(含)稀土矿物主要是榍石、褐帘石、褐钇铌矿和锆石,其次为少量钍石、独居石、磷钇矿、含稀土萤石和氟碳酸盐矿物等; 斜长石和黑云母对岩石中的REE富集也有一定贡献。

  • (2)本文测得黑云二长花岗岩的锆石U-Pb年龄为50.33±0.3 Ma(MSWD=0.15),与前人测得数据相似,该岩体是目前发现的最年轻的iREE成矿母岩。

  • (3)岩石具有高硅高碱、低铁低镁的特征,A/CNK>1.1(1.25~1.57),具有高钾—强过铝质钙碱性花岗岩的特征。岩浆的分异作用与岩石中REE含量的变化相关性较弱; 岩浆岩演化过程中产生的热液作用是决定iREE(甚至iHREE)成矿的关键。

  • (4)(含)稀土矿物的种类和数量通常决定了岩石甚至iREE的稀土配分类型。热液作用下产生的新的(含)稀土矿物因HREE相对较富、化学元素组成较复杂和化学键强度较弱,相对于早期形成的矿物更易于在自然风化作用下解离,是形成iREE(特别是iHREE)的首要来源。

  • (5)邦棍尖山花岗岩中,榍石、褐帘石、含稀土萤石和氟碳酸盐矿物,是REE的主要来源; 其次,斜长石和黑云母对成矿亦有贡献。这些矿物因LREE含量相对较高,在自然风化作用下解离后形成iLREE矿。

  • 致谢:感谢审稿专家提出的宝贵意见。感谢杨岳清老师、王瑞江老师、赵芝和杨武斌老师在野外工作和室内研究分析、文章撰写过程中提供的帮助并给出建设性的指导建议,在此一并表示衷心感谢!

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