2. 中国科学院大学, 北京 100049;
3. 中国科学院地球科学研究院, 北京 100029;
4. 新疆地矿局第三地质大队, 库尔勒 841000
2. University of Chinese Academy of Sciences, Beijing 100049, China;
3. Innovation Academy for Earth Science, Chinese Academy of Sciences, Beijing 100029, China;
4. No.3 Geological Party, Xinjiang Bureau of Geology and Mineral Exploration and Development, Korla 841000, China
稀有金属(包括锂、铍、铌、钽、铯、锆、铪和铷)是重要的战略金属,广泛应用于国防、航天、航空等工业领域(Linnen et al., 2014; Nassar, 2017; Kaeter et al., 2018)。近年来,稀有金属因其重要战略意义而被中国和欧、美、日等国列入“战略与关键金属”清单中(Linnen et al., 2012; 张辉等,2019)。其中稀有金属锂元素被称为“绿色高能金属”、“白色石油”。随着新能源汽车和储能技术的高速发展,未来世界对锂资源的需求将愈演愈烈,亟需在锂矿资源上找到突破(王秋舒和元春华,2019)。花岗伟晶岩是稀有金属的重要来源,花岗伟晶岩型稀有金属矿床也是目前矿床学研究的热点(Linnen et al., 2012; Chakhmouradian et al., 2015; Kaeter et al., 2018; Yin et al., 2020)。稀有金属花岗伟晶岩成岩成矿年龄的确定是此类矿床研究的重要内容(周振华等,2016;王倩等,2019)。
稀有金属花岗伟晶岩测年的方法较多,有锆石U-Pb(任宝琴等,2011;Zhou et al., 2015, 2018; 马占龙等,2015;杨红等,2017)、白云母和微斜长石Ar-Ar (Zhou et al., 2015, 2018; Chen et al., 2000)、白云母和微斜长石K-Ar (邹天人等,1986;)和全岩Rb-Sr (Clark, 1982; 邹天人等,1986;朱永峰和曾贻善,2002;Zhu et al., 2006)等定年方法。其中,锆石U-Pb年龄一般解释为岩浆岩结晶年龄,而蜕晶化的锆石U-Pb年龄记录的是岩浆锆石蜕晶化后经流体交代作用及重结晶作用导致U-Pb同位素系统重置的时间(杨红等,2017)。云母等含钾矿物的K-Ar和Ar-Ar法测定的年龄可能代表岩浆结晶结束的年龄或后期多期次热事件的年龄(Zhu et al., 2006;李建康等, 2006a, b)。铌钽铁矿U-Pb定年(Romer et al., 1996b; Lupulescu et al., 2011; 钟龙等,2011;Li et al., 2019; Feng et al., 2020; Wang et al., 2020)在近些年取得巨大进展,该方法不存在继承矿物影响,被认为是目前伟晶岩定年最可靠的方法。锡石U-Pb定年方法多用于确定锡多金属矿床的成矿时代,但近年来越来越多的含锡石稀有金属伟晶岩矿床用锡石U-Pb定年法来确定伟晶岩型稀有金属矿床的成矿时代(袁顺达等,2010;张东亮等,2011;Yan et al., 2018; 代鸿章等,2018;Kendall-Langley et al., 2020;费光春等,2020; 许家斌等,2020),如:松潘-甘孜造山带的李家沟(许家斌等,2020)、党坝(费光春等,2020)、甲基卡308号脉(代鸿章等,2018),西昆仑-喀喇昆仑成矿带的大红柳滩稀有金属矿床(Yan et al., 2018)都使用了锡石U-Pb定年,且可与铌钽矿U-Pb定年结果相互验证。
然而,不同定年方法在同一个矿床中得出的定年结果往往差异很大。例如:可可托海3号脉中锆石U-Pb年龄为180~220Ma (Wang et al., 2007; 陈剑锋,2011;周起凤,2013),铀细晶石U-Pb年龄为196.4Ma (邹天人等,1986),白云母K-Ar年龄为160~292Ma (邹天人等,1986),微斜长石K-Ar年龄为120Ma (邹天人等,1986),白云母Ar-Ar年龄为160~292Ma (陈富文等,1999;周起凤,2013),钾长石Ar-Ar年龄为148Ma (陈富文等,1999),铌钽铁矿U-Pb年龄为218Ma (Che et al., 2015)、205.6Ma (王倩等,2019),辉钼矿Re-Os年龄为210~208Ma (Liu et al., 2014)及Rb-Sr等时线年龄为331.9Ma (邹天人等,1986)、238Ma (朱永峰和曾贻善,2002)、218.4Ma (Zhu et al., 2006)。这可能和不同定年体系的适用条件有关。这些方法中哪种更合理、更可靠?哪些方法给出的结果是可以相互验证的?不同方法给出的结果出现差异的原因是什么?为了综合评价稀有金属伟晶岩不同定年方法,我们选择阿尔金中段吐格曼北锂铍矿床含矿伟晶岩分别开展锆石、锡石、铌钽铁矿及白云母不同方法的测年对比研究,以期了解不同测年方法的使用条件,同时也对获得的数据进行合理解释。
1 阿尔金中段吐格曼花岗伟晶岩型稀有金属矿床特征 1.1 区域地质背景阿尔金造山带位于青藏高原北缘,地处塔里木板块、柴达木地块及祁连-昆仑造山带之间(图 1),是由早古生代板块(或地块)之间相互俯冲-碰撞形成的复杂构造带,在中、新生代又被走滑断裂所切割,整个造山带由不同时期、不同构造层次和形成于不同构造环境的地质体拼合而成(郑剑东,1991;车自成等, 1995, 1998;刘良等, 1996, 1999;郭召杰等,1998;Zhang et al., 1999, 2001; 周勇和潘裕生,1999;徐兴旺等,2019)。
阿尔金中段吐格曼地区位于新疆若羌县城南侧的阿尔金山,构造上属于阿中地块(图 1)。吐格曼地区出露的地层主要有新太古界米兰岩群(Ar1-2M)、中元古界阿尔金岩群(Pt2A)与复理石建造(fw(Pt2))、长城系贝壳滩组(Chb)与蓟县系金雁山组(Jxj)(图 2)。其中,米兰岩群为一套强烈变形变质的碎屑岩、碳酸盐岩夹火山岩建造,普遍含有蓝晶石、石榴石、十字石、夕线石等变质矿物,主要岩石类型包括石榴黑云斜长片麻岩、蓝晶石榴黑云斜长片麻岩、十字夕线蓝晶黑云片岩、石榴斜长角闪岩、大理岩、石英岩与变粒岩等,分布于研究区的东南部;阿尔金岩群广泛出露于研究区的中部及西南部,主要为一套由变质碎屑岩、碳酸盐岩和变质火山(碎屑)岩组成的绿片岩相-角闪岩相变质岩系;中元古界复理石建造为英格里克构造蛇绿混杂岩的组成部分,呈北东-南西向分布于研究区西南、东北部,为主要由斜长二云石英片岩、石榴石十字石二云石英片岩、黑云斜长变粒岩与二云母片岩等构成的绿片岩相-角闪岩相变质岩系,其与南北两侧的米兰岩群和阿尔金岩群地层间为断层接触;长城系贝壳滩组由灰白、灰-深灰色中厚层状石英岩、黑云石英岩、二云石英片岩、变质粗粒长石岩屑砂岩与斜长白云母石英片岩等绿片岩相变质岩组成;区内蓟县系金雁山组分布于库木加克沟两侧,大致呈近东西向展布,岩性主要为一套大理岩(徐兴旺等,2019)。
吐格曼地区花岗岩发育,岩石类型主要有片麻状黑云二长花岗岩、二长花岗岩、二云母花岗岩与黑云斜长花岗岩,规模较大的岩体从北向南依次主要分布有库鲁赛、阿亚格、托巴、吐格曼、萨拉姆五个岩体。其中,吐格曼岩体是2018年野外地质调查过程新识别的大型层状岩体(徐兴旺等,2019),岩体产出于中元古界复理石建造中(图 2);岩体层状构造发育,包括不同矿物组成花岗岩的岩性层及其内部矿物分带而显示的层状构造;岩体岩石类型多样,有黑云母花岗岩、二云母花岗岩、白云母花岗岩、及钠长花岗岩;层状黑云母花岗岩分布于岩体的外侧与边缘(图 2),而其它岩性层构成的淡色层状花岗岩体是岩体的主体;层状淡色花岗岩中发育从二云母花岗岩到白云母花岗岩和钠长花岗岩的连续结晶分异与演化的多个韵律组合。钠长花岗岩层顶部可发育电气石与石榴子石相对富集的钠长花岗岩(徐兴旺等,2019)。
1.2 矿床地质特征阿尔金中段吐格曼地区是稀有金属锂铍元素成矿的有利地区,是花岗伟晶岩型稀有金属矿床成矿与找矿研究的新区(徐兴旺等,2019)。近年来新发现了吐格曼铍锂矿、吐格曼北锂铍矿和瓦石峡南锂铍矿3个矿床(徐兴旺等,2019)。其中吐格曼铍锂矿和吐格曼北锂铍矿分别位于吐格曼岩体的中心地带和北接触带(图 2)。
吐格曼北锂铍矿位于吐格曼岩体的北接触带(图 2),为花岗伟晶岩型锂铍矿。锂铍花岗伟晶岩脉发育于二云母花岗岩及其北侧的石榴子石云母石英片岩中。区内发现27条锂铍花岗伟晶岩脉,脉带整体呈东西向展布,各脉体规模大小不一,长50~700m,宽1~35m,脉体呈透镜状和树枝状产出(图 3)。主要由钠长石、钾长石、白云母、石英、电气石、锂辉石和绿柱石等矿物组成,含少量铌钽铁矿、磷灰石、独居石和锆石等副矿物。根据矿物组成,矿区伟晶岩可分为钠长石-锂辉石伟晶岩、白云母-钠长石-锂辉石伟晶岩、钾长石-绿柱石伟晶岩和白云母-锡石伟晶岩四种类型。下面重点介绍ρ31、ρ38与ρ87脉体的产出特征。
① 新疆维吾尔自治区地质矿产勘查开发局第三地质大队. 2016.新疆若羌县塔什萨依一带铅锌、锰矿调查评价报告. 1-240
1) ρ31花岗伟晶岩特征(图 4a,b):脉体呈北东向产出,产状150°∠53°,长200m、宽3~6m,脉体截切地层片理。ρ31伟晶岩脉内部结构分带清楚,中心发育白云母-石英-锂辉石伟晶岩,两侧均为钠长花岗岩带,局部也有细长的锂辉石脉体,钠长花岗岩带。脉体整体向东延伸,锡石产出于脉体边部的上盘(图 4c)。
2) ρ38花岗伟晶岩特征:ρ38北段发育白云母-钠长石-锂辉石伟晶岩,脉体产状89°∠80°,长210m、宽1.5m;ρ38南段伟晶岩脉体产状170°∠35°,长198m、宽约2m,其形态为倒立树枝状(由上向下分叉)。该脉中部发育大量钾长石,为浅黄色的钾长石伟晶岩,上部和下部分别发育钾长石-绿柱石伟晶岩和钠长石-锂辉石伟晶岩(图 4d-f)。
3) ρ87花岗伟晶岩特征:ρ87号伟晶岩脉位于矿区南侧,脉体产状平缓、明显截切近直立的地层片理。花岗伟晶岩脉内部结构分带(图 5a,b)共分为四个带,包括白云母-石英带(Ⅰ)、文象带(Ⅱ)、钠长石-石英-锂辉石带(Ⅲ)、细晶岩带(Ⅳ)。在细晶花岗岩带中见交代的含铌钽铁矿-白云母-石英伟晶岩脉(图 5c, d)。
矿区发现的27条花岗伟晶岩型锂铍矿体,共生Nb、Ta、Rb、Cs;Li2O品位0.57%~6.1%,平均品位1.1%,资源量达2万吨;BeO品位0.04%~2.6%,平均品位0.47%,资源量达0.37万吨;Nb2O5品位0.014%~0.029%;Ta2O5品位0.008%~0.078%;Rb2O品位0.051%~0.27%;Cs2O品位0.04%~1.96%。初步估算锂铍金属资源量已达中型矿床规模。
2 样品选择及岩石学特征针对吐格曼北锂铍矿床伟晶岩样品开展了系统的同位素年代学研究。采集样品(表 1)后,对38号脉白云母-钠长石-锂辉石伟晶岩样品进行锆石U-Pb测试(1件:18AE18)和白云母40Ar/39Ar测试(1件:18AE18)、对31号脉白云母-锡石伟晶岩样品进行锆石U-Pb测试(1件:18AE30)、锡石U-Pb测试(1件:19AE43)以及对87号脉含铌钽铁矿-白云母-石英伟晶岩样品进行铌钽铁矿U-Pb测试(1件:19TC87)。具体采样位置见图 3。
白云母-钠长石-锂辉石伟晶岩(18AE18、18AE30)为灰白色,伟晶结构,块状构造;主要矿物组成为石英(10%~15%)、锂辉石(70%~85%)、白云母(~5%)和钠长石(5%~10%)(图 4f、图 6)。手标本中石英呈无色透明,他形粒状,粒径1 ~ 2cm;锂辉石呈灰白色板状、柱状,长度为1~13cm,镜下可见发生碎裂化锂辉石;白云母为亮白色片状,片状部分最长可达2cm,白云母片状晶体发生构造变形与热液蚀变;钠长石白色板柱状,自形程度较好,长度为1 ~ 2cm。
白云母-锡石伟晶岩(19AE43)为伟晶结构,块状构造;主要矿物组成为石英(50%~60%)、白云母(15%~25%)和锡石(15%~25%)。其中锡石集合体长度范围为1~4cm,呈短柱状、自形,表面光滑,呈铁黑色至褐黑色,多与白云母、石英共生(图 4c)。
含铌钽铁矿-白云母-石英伟晶岩(19TC87)为伟晶结构,块状构造;主要矿物组成为石英(50%~65%)、白云母(20%~30%)和铌钽铁矿(15%~20%),其中铌钽铁矿集合体宽1~2mm、长1~2cm,呈长柱状,多与白云母、石英共生(图 5c)。
3 测试方法 3.1 锆石U-Pb测年单颗粒锆石分选在河北区域地质矿产调查研究所实验室使用常规的重选和磁选技术完成。锆石制靶和U-Pb同位素定年分析在武汉上谱分析科技有限责任公司利用LA-ICP-MS分析完成。将晶型较好的锆石样品颗粒和锆石标样粘贴在环氧树脂靶上,抛光使其曝露一半晶面。然后进行锆石透反射光显微照相和阴极发光图像分析,选择适宜的测试点位(图 7)。详细的仪器参数和分析流程见文献(Zong et al., 2017)。GeolasPro激光剥蚀系统由COMPexPro102 ArF193nm准分子激光器和MicroLas光学系统组成,ICP-MS型号为Agilent 7700e。激光剥蚀过程中采用氩气为补偿气、氦气作载气以调节灵敏度,二者在进入ICP之前通过一个T型接头混合,激光剥蚀系统配置有信号平滑装置(Hu et al., 2015)。本次分析的激光束斑和频率分别为32μm和5Hz。U-Pb同位素定年和微量元素含量处理中采用锆石标准91500和玻璃标准物质NIST610作外标分别进行同位素和微量元素分馏校正。每个时间分辨分析数据包括大约20~30s空白信号和50s样品信号。对分析数据的离线处理(包括对样品和空白信号的选择、仪器灵敏度漂移校正、元素含量及U-Pb同位素比值和年龄计算)采用软件ICPMSDataCal (Liu et al., 2008, 2010)完成。锆石样品的U-Pb年龄谐和图绘制和年龄加权平均计算采用Isoplot/Ex_ver3 (Ludwig, 2003)完成。
锡石单矿物分选在中国科学院地质与地球物理研究所岩矿制样与分析实验室完成。选取新鲜的白云母-锡石伟晶岩样品进行机械破碎,经磁选、重选后在双目显微镜下挑选得到晶形较好的锡石。将挑选的锡石粘在环氧树脂上,待树脂固化后刨磨至大部分锡石颗粒露出。
锡石制靶和U-Pb同位素定年在天津地质调查中心分析测试室完成。所用仪器为Neptune多接收电感耦合等离子体质谱仪和193nmArF准分子激光取样系统(LA-MC-ICP-MS)。实验流程具体如下:根据反射光和透射光图像,避开包裹体和裂纹,选择锡石颗粒的合适区域,以减少普通铅的影响(李惠民等,2009; Yuan et al., 2011)。利用193nmFX激光器对选择好的锡石区域进行剥蚀,激光斑束为78μm,频率为15Hz,样品信号采集时间为26s,激光剥蚀物质以He为载气送入Neptune (MC-ICP-MS),利用动态变焦扩大色散使质量数相差很大的U-Pb同位素可以同时接收,从而对U-Pb同位素进行测定(Yuan et al., 2011)。数据处理采用Isoplot程序进行分析和作图(Ludwig, 2003)。通过U-Pb Tera-Wasserburg年龄谐和图的下交点来计算锡石年龄。Yuan et al. (2011)中标样AY-4数据为159.9±1.9Ma,本次测试时标样数据为158.1±4.1Ma,二者在误差范围内一致,数据可靠。
3.3 铌钽铁矿U-Pb测年铌钽铁矿单矿物分选在河北区域地质矿产调查研究所完成。选取新鲜的含铌钽铁矿-白云母-石英伟晶岩样品进行机械破碎,经磁选、重选后在双目显微镜下挑选得到晶形较好的铌钽铁矿。将挑选的铌钽铁矿粘在环氧树脂上,待树脂固化后刨磨至大部分铌钽铁矿颗粒露出。铌钽铁矿反射光、背散射(BSE)图像的拍摄在中国科学院地质与地球物理研究所矿产资源研究院重点实验室完成。
铌钽铁矿的U-Pb年代学测定由南京大学内生金属矿床成矿机制研究国家重点实验室电感耦合等离子体质谱Thermo Fisher Scientific iCAP-Q型ICP-MS与RESOlution S155型193nm的ArF准分子激光器联用完成,详细的分析步骤参见Che et al. (2015)。铌钽矿定年采用铌铁矿Coltan139作为外部标准进行校正。激光束斑直径为67μm,频率4Hz,每个分析点的气体背景采集为20s,信号采集时间50s,204Pb、206Pb和208Pb驻留时间为15ms,207Pb为30ms,232Th和238U为10ms,其他元素均为6ms。每测定8个样品点,分析2次年龄标样(Coltan 139)和1次NIST610。数据分馏和校正处理采用是ICPMSDataCal程序(Liu et al., 2008)。处理后利用Isoplot 4.15对U-Pb同位素年龄进行计算和作图(Ludwig, 2003)。
3.4 白云母Ar-Ar测年白云母单矿物分选在河北区域地质矿产调查研究所完成。将选定的样品(18AE18)清洗晒干并逐步粉碎至40~60目,之后在双目镜下人工挑选白云母,在40~60目颗粒级别上获得均匀的样品。置于去离子水中超声清洗5次,每次20min,之后置于丙酮中再超声清洗3次,每次20min。
白云母Ar-Ar同位素定年在核工业北京地质研究院分析测试研究中心完成。称取适量40~60目粒级的岩石或矿物样品进行清洗,用铝箔将每个样品单独包装,将多个样品用石英管融封,外面包裹厚1mm的镉皮,在中国原子能科学研究院快中子反应堆照射24小时。照射后的样品在超高真空析氩系统双真空炉中进行阶段升温融样,用含有锆铝泵的NGP REP SYSTEM型纯化系统纯化各阶段释放的气体。室温下40Ar本底小于1.0E-15mol,1300℃时,本底小于1.0E-14mol。
用Helix SFT型惰性气体质谱仪静态测定氩的同位素比值。用阶段升温各温度段获得的年龄及累计39Ar百分比含量及ArArCALC ver2.4软件,绘制年龄谱图,并用加权法计算出坪年龄,用直线拟合方法计算出40Ar/39Ar的初始比值及等时线年龄。用于中子通量监测的标准样品为:GBW04418角闪石,其K=0.729±0.005%,Ar=109.06×10-6 (CCSTP/g),年龄值为2060±8Ma。ZBH-25黑云母,其K=7.599%,Ar=1.8157×10-9 (mol/g),年龄值为132.9±1.3Ma。
4 分析结果 4.1 锆石U-Pb年龄ρ31白云母-钠长石-锂辉石伟晶岩(18AE30)样品中锆石长度在50~100μm之间,宽度在50~70μm之间,长宽比为1~1.5之间,锆石主要以半自形-不规则次圆状为主。锆石多无色、透明,晶形较好,少数锆石具碎裂现象,锆石CL图像多呈灰黑色模糊海绵状(图 7a)。锆石的LA-ICP-MS U-Pb分析结果显示:该伟晶岩锆石U、Th与Pb含量分别为:4148×10-6~10066×10-6、9×10-6~29×10-6、311×10-6~731×10-6,Th/U值0.002~0.003。16个锆石的206Pb/238U年龄在450.6~468Ma之间,在误差范围内基本一致,206Pb/238U谐和年龄为458.7±2.3Ma。数据置信度95%,数据可信度高(表 2、图 7c)。
ρ38白云母-钠长石-锂辉石伟晶岩(18AE18)样品中锆石长度在75~200μm之间,宽度在60~130μm之间,长宽比为1~1.7之间,锆石主要以半自形、规则-次圆状为主。锆石多无色、透明,晶形较好。CL图像多呈灰黑色模糊海绵状,少量锆石CL图像呈灰色、发育微弱环带构造(图 7b)。锆石的LA-ICP-MS U-Pb分析结果显示:该伟晶岩锆石U、Th与Pb含量分别为:2219×10-6~14964×10-6、6×10-6~72×10-6、161×10-6~1129×10-6,Th/U值0.002~0.005。10个锆石的206Pb/238U年龄在447.5~464.9Ma之间,在误差范围内基本一致,206Pb/238U谐和年龄为454.7±4.0Ma。数据置信度95%,数据可信度高(表 2、图 7d)。
2个样品(18AE30与18AE18)中的锆石Th/U比值较低(分别为0.002~0.003、0.002~0.005),平均值分别为0.0026、0.0034,均小于0.1。2个样品中锆石具高的稀土总量,平均值分别为2575×10-6、739×10-6 (表 3)。球粒陨石标准化稀土元素配分曲线整体呈左倾趋势,重稀土明显富集、轻稀土相对亏损。2个样品中除个别锆石外,稀土配分曲线具有的正Ce异常负Eu异常,其中样品18AE30稀土配分曲线具明显的正Ce异常(平均值为2.05)和负Eu异常(图 8a)。与典型岩浆锆石相比,样品锆石的轻稀土含量升高、曲线左倾趋势变缓(Hoskin and Ireland, 2000; Belousova et al., 2002; Rubatto, 2002; Hoskin and Schaltegger, 2003; Liu and Liou, 2011)。2个样品的锆石具异常高的P(分别为613×10-6~2463×10-6、665×10-6~1239×10-6)、Y (1215×10-6~4844×10-6、171×10-6~1344×10-6)、Yb (424×10-6~3841×10-6、167×10-6~634×10-6)与Hf (10237×10-6~50286×10-6、11427×10-6~60387×10-6)含量、及高的(Sm/La)N值与低的Ce/Ce*值(表 3),显示出典型的热液锆石特征(图 8b;Hoskin, 2005)。
白云母-锡石伟晶岩样品(19AE43)中锡石为深褐色-黑色、半透明、自形-半自形晶体,透反射图像显示其内部结构较简单,环带不发育,少见矿物包裹体(图 9a,b)。测点共39个,238U/206Pb值变化范围为2.73~13.04,238U/207Pb值变化范围为4.90~176.1,206Pb/207Pb值变化范围为1.82~14.24 (表 4),锡石238U/206Pb-207Pb/206Pb谐和年龄为468±8.7Ma (图 9c;MSWD=1.1,N=39)。
含铌钽铁矿-白云母-石英伟晶岩样品(19TC87)中铌钽铁矿为黑色、半透明、自形-半自形晶体,反射光和背散射图像显示其内部结构较简单,环带不发育(图 10a,b)。铌钽铁矿206Pb/238U值变化范围为0.072~0.078,207Pb/235U值变化范围为0.541~0.625,207Pb/206Pb值变化范围为0.048~0.073,铌钽铁矿颗粒具有较低的U含量(38×10-6~527×10-6)、较低的Th含量(0.02×10-6~0.27×10-6),Th/U的范围为0.0003~0.0012 (表 5)。铌钽铁矿共39个测点产生的207Pb/235U-206Pb/238U谐和年龄为464.1±2.7Ma (图 10c,MSWD=5.2,N=39),数据可靠。
白云母样品的40Ar/39Ar阶段升温加热分析结果见表 6,图 11给出了坪年龄谱图、等时线年龄图,所有的误差置信水平为2σ。采用Isoplot3.0软件(Ludwig, 2003)进行数据处理与作图,由表 6和图 11可知,白云母样品9个阶段加热分析过程中,39Ar在(0%~100%)的释放区域内呈现一条平坦的Ar-Ar坪年龄谱图(图 11a),坪年龄为350.2±1.6Ma,这表明样品K和放射性40Ar*分布均匀,且自矿物生成以来保持良好的封闭状态,没有受到明显的后期热扰动。对参与坪年龄计算的数据进行39Ar/36Ar-40Ar/36Ar等时线拟合处理,结果构成了线性关系较好的等时线(图 11b),等时线年龄为351.4±2.7Ma (MSWD=5.1),和坪年龄在误差范围内一致,证实白云母定年结果可靠且具有地质意义。
稀有金属花岗伟晶岩的成因目前存在是形成于花岗岩浆的结晶分异还是形成于地壳深熔成因的争论(Černy, 1992; Shaw et al., 2016; 张辉等,2019)。基于大部分花岗伟晶岩与花岗岩在空间和成因上有一定联系的因素(Černy et al., 2012; Grew, 2002; London and Evensen, 2002),绝大多数研究者认为花岗伟晶岩为花岗岩结晶分异成因(Jahns and Burnham, 1969; London and Morgan, 2012; Simmons and Webber, 2008)。即花岗伟晶岩浆为花岗岩分异结晶的残余岩浆(Simmons and Webber, 2008),是经历了二云母花岗岩、白云母花岗岩和钠长花岗岩浆分异结晶后的残余岩浆(London and Evensen, 2002; London, 2008; 王汝成等,2017;吴福元等,2017;Liu et al., 2019; Wu et al., 2020; Xie et al., 2020)。
花岗伟晶岩中的矿物按成因划分可分为两种:新生矿物和残留矿物。前者指由于花岗伟晶岩浆结晶过程新形成的矿物,花岗伟晶岩中绝大多数矿物为新生矿物,包括钾长石、钠长石、白云母、石英、磷灰石、及锂辉石、锂云母、绿柱石、金绿宝石与铌钽铁矿等稀有金属矿物。这些新生矿物由于结晶温度与元素在熔体中溶解度的不同可在花岗伟晶岩内部分带产出(Jahns and Burnham, 1969; Jahns, 1982; Burnham and Nekvasil, 1986; London, 2008; Simmons et al., 2012)。这些新生矿物记录了花岗伟晶岩的形成与演化信息,可用于研究与测定花岗伟晶岩的形成时代。
花岗伟晶岩中锆石、夕线石、蓝晶石、堇青石和红柱石可能多为残留矿物(Wu et al., 2020)。花岗伟晶岩中的残留锆石由于高的U、Th含量多表现出显著的蜕晶化。Zhou et al. (2015)、徐兴旺等(2019)、王倩等(2019)研究结果显示这种蜕晶化的残留锆石部分具有热液锆石的特征,其可能是岩浆锆石蜕晶化后经流体交代作用及重结晶作用导致U-Pb同位素系统重置的结果。
近年来,除了锆石以外,大量与成矿有关的含U副矿物被用来直接进行U-Pb定年,如锡石、独居石、磷灰石、石榴子石、黑钨矿、铌钽矿等,对相关矿床的研究有了更深入的认识。自Marini and Botelho (1986)最早尝试利用锡石U-Pb同位素体系对锡矿床进行年龄测定以来,该方法先后被国内外学者应用于不同锡矿床的成矿年代学研究(Gulson and Jones, 1992; 刘玉平等,2007;Yuan et al., 2008, 2011)。其中锡石属于金红石族矿物,具有比较稳定的化学结构,其晶格内一般可容纳高含量的U并且不易受后期热液作用的影响(Jiang et al., 2004; 刘玉平等,2007)。锡石作为伟晶岩型稀有金属矿床的矿石矿物,其结晶年龄直接代表了锡石结晶的年龄和伟晶岩的形成时代,以其同位素年龄来确定稀有金属矿床的形成时代,与脉石矿物、蚀变矿物(如云母、闪石)以及全岩同位素数据相比具有优越性。因此比较适合作为伟晶岩型稀有金属矿床的直接定年矿物。据前人研究,在冷却速率为10℃/Myr的体系中、非超高温条件下,锡石封闭温度为600~800℃(张东亮等,2011)。锡石U-Pb法是一种准确测定锡石结晶年龄的有效方法(McNaughton et al., 1993; 刘玉平等,2007;Yuan et al., 2008, 2011; 袁顺达等,2010;张东亮等,2011)。
铌钽铁矿族矿物普遍存在于各种稀有金属伟晶岩矿床(Černy and Lenton, 1995; Selway et al., 2005)、花岗岩有关的热液型钨锡(Lerouge et al., 2007)及稀土(Möller, 1989)矿床中。确定铌钽铁矿族矿物的年龄可以为多种矿床类型提供重要的年龄限制,特别是与富含稀有元素的花岗岩和伟晶岩有关的矿床(Melleton et al., 2012)。自Aldrich et al. (1956)建立铌钽铁矿U-Pb定年方法以来,一些学者开始尝试使用同位素稀释热电离质谱法(ID-TIMS, Romer and Wright, 1992; Romer and Smeds, 1994, 1996, 1997; Romer and Lehmann, 1995; Romer et al., 1996b)和多接收电感耦合等离子体质谱法(LA-MC-ICP-MS, Smith et al., 2004; Dill et al., 2007; Melcher et al., 2008; Dewaele et al., 2011; Deng et al., 2013; Che et al., 2015)测定铌钽铁矿U-Pb年龄,并取得了可靠的年龄数据。例如,Camacho et al. (2012)对加拿大东南部著名的Tanco和Silverleaf稀有金属矿床进行了年代学研究,获得花岗伟晶岩中钽铁矿U-Pb年龄为2641±3Ma,与磷灰石Pb-Pb年龄2657±18Ma、白云母和钠长石Rb-Sr等时线年龄~2630Ma在误差范围内一致。
白云母Ar-Ar定年已发展为同位素地质年代学主要的研究手段之一,也是矿床年代学研究的主要技术手段。白云母Ar-Ar定年也应用到了稀有金属矿床的年代学研究(陈郑辉等,2006;李建康等, 2006a, b,2009,2013;李建康,2006; 张泽等,2019),如Wang et al. (2003)通过对伟晶岩型稀有金属矿床中白云母的Ar-Ar法同位素定年研究,首次在阿尔泰中部的大喀拉苏大型稀有金属矿床和小喀拉苏稀有金属矿床获得了新的同位素年龄数据,其坪年龄分别为248.4±2.1Ma和233.8±0.4Ma,从而证实了印支期稀有金属成矿作用的存在,提出了伟晶岩型矿床形成于多个时代,且稀有金属成矿作用主要发生在海西期造山运动之后的看法。陈富文等(1999)对可可托海Ⅰ带和Ⅴ带中白云母进了Ar-Ar年龄测试,分别获得39Ar/36Ar-40Ar/36Ar等时线年龄177.9±0.03Ma、176.9±1.8Ma,认为是由花岗质岩浆在地下深处封闭体系中经过漫长的岩浆结晶分异形成。Zhang et al. (2014)通过对雪宝顶Sn-W-Be矿床中白云母和锡石分别进行了Ar-Ar和U-Pb年龄测试,获得白云母40Ar/39Ar年龄为194.5±1.0Ma、锡石U-Pb谐和年龄为193.6±6Ma,李建康等(2007)获得了白云母40Ar/39Ar年龄为189.9±1.8Ma,锡石U-Pb与白云母40Ar/39Ar年龄在误差范围内基本一致。但有学者指出大喀拉苏(任宝琴等,2011;Liu et al., 2018)伟晶岩形成时代是二叠纪,而可可托海3号脉形成于三叠纪(Zhu et al., 2006; Wang et al., 2007; 陈剑锋,2011;Che et al., 2015)。无论是大喀拉苏、小喀拉苏还是可可托海3号脉,利用含钾矿物的Ar-Ar定年结果比锆石、铌钽矿U-Pb定年结果至少年轻数十百万年。
综上所述:不同定年体系因为封闭条件不一样,测年对象的差异性,导致了对年龄数据没有很好的、合理的解释。此外,多数伟晶岩利用含钾矿物的Ar-Ar定年结果比锆石、铌钽矿U-Pb定年结果至少年轻数十百万年,这可能是由于这些伟晶岩经历过后期热液活动的改造,但在区域内没有发现伟晶岩经历过后期热液活动的岩相学证据,造成了含钾矿物Ar-Ar定年不足为信的假象。
5.2 吐格曼北锂铍矿床成矿时代及其区域成矿学意义吐格曼北锂铍矿床ρ31白云母-锡石伟晶岩样品中锡石U-Pb测年的T-W图解中下交点的年龄为468±8.7Ma (图 9c,MSWD=1.1,N=39),该结果能代表锡石结晶年龄。由于锡石封闭温度较高(600~800℃,张东亮等,2011),所以锡石结晶年龄可代表伟晶岩浆结晶阶段的年龄。
ρ87含铌钽铁矿-白云母-石英伟晶岩中铌钽铁矿物,常与白云母和石英共生。铌钽铁矿U-Pb年龄464.1±2.7Ma (MSWD=5.2,N=39)可约束稀有金属伟晶岩的岩浆结晶年龄。
2条脉体(ρ31、ρ38)白云母-钠长石-锂辉石伟晶岩样品中锆石U-Pb年龄分别为458.7±2.3Ma (MSWD=7.2, N=16)、454.7±4.0Ma (MSWD=8.0, N=10)。锆石的CL图像(图 7a, b)表明样品中的锆石多呈黑色模糊海绵状,仅部分颗粒见弱的薄边,这些特征表明其在岩浆阶段由于高U含量和晚期流体的作用,锆石经历了蜕晶化和重结晶(Dickin, 1995; Romer et al., 1996a)。另外,锆石(Sm/La)N-Ce/Ce*图解(图 8b)显示2个样品中锆石(18AE18、18AE30)均为热液成因,说明该锆石为岩浆锆石在伟晶岩热液阶段U-Pb同位素系统重置的锆石(杨红等,2017),意味着锆石谐和年龄记录的是岩浆锆石蜕晶化后经流体交代作用及重结晶作用导致U-Pb同位素系统重置的时间。
吐格曼北锂铍矿床白云母-锡石伟晶岩中锡石U-Pb年龄、含铌钽铁矿-白云母-石英伟晶岩中铌钽铁矿U-Pb年龄(分别为468±8.7Ma、464.1±2.7Ma)在误差范围内一致;2条伟晶岩脉(ρ31、ρ38)锆石U-Pb年龄相近,并可与该矿床南侧的吐格曼铍锂矿花岗伟晶岩的年龄459.9±3.7Ma对比(徐兴旺等,2019)。鉴于锡石封闭温度较高、可代表伟晶岩浆早期结晶阶段的年龄,铌钽铁矿可能为岩浆-热液过渡阶段的产物,而蜕晶化的锆石记录的是岩浆锆石蜕晶化后经流体交代作用及重结晶作用导致U-Pb同位素系统重置的时间。
由此可以认为,吐格曼北锂铍矿床稀有金属伟晶岩的形成年龄为468~454Ma (图 12),持续时间为14Myr。这与许多伟晶岩结晶时间持续10~20Myr (Chen et al., 2000; Wang et al., 2007; Lv et al., 2012; Zhou et al., 2015)的特征是一致的,尽管模拟实验结果显示一个花岗岩体与花岗伟晶岩脉的结晶成岩时间一般小于几个百万年(Coleman et al., 2004; Matzel et al., 2006; Michel et al., 2008; Sirbescu et al., 2008; London et al., 2020)。
ρ38白云母-钠长石-锂辉石伟晶岩中白云母Ar-Ar测年的测试结果显示:白云母40Ar/39Ar坪年龄为350.2±1.6Ma (MSWD=4.7),39Ar/36Ar-40Ar/36Ar等时线年龄为351.4±2.7Ma (MSWD=5.1),该年龄较含矿伟晶岩中锆石、锡石与铌钽铁矿的U-Pb年龄年轻约110Ma。由于吐格曼北锂铍矿床中白云母褶曲变形强烈(图 6),本文认为该期白云母可能与含矿伟晶岩脉遭受到后期的构造运动有关,研究区在早石炭世时可能存在构造运动叠加的热事件。
5.3 不同方法结果对比与启示如上所述,吐格曼北锂铍矿床不同矿物记录了不同岩浆-热液阶段的时间,其中锡石年龄代表伟晶岩浆早期结晶阶段的年龄,铌钽铁矿可能为岩浆-热液过渡阶段的产物,而蜕晶化的锆石记录的是岩浆锆石蜕晶化后经流体交代作用及重结晶作用导致U-Pb同位素系统重置的时间。这些年龄在误差范围内是一致的,综合考虑分析结果的误差可以确定伟晶岩矿床形成的时间;而白云母Ar-Ar年龄记录的是最晚期的构造叠加热事件时间。前人关于稀有金属花岗伟晶岩的定年结果(表 7)也能佐证我们的观点:(1)稀有金属花岗伟晶岩的锆石U-Pb与铌钽铁矿U-Pb法所测得年龄基本一致,如Bohemian伟晶岩(捷克)锆石U-Pb年龄(480Ma,Glodny et al., 1998)与铌钽铁矿U-Pb年龄(480Ma,Glodny et al., 1998)、小秦岭伟晶岩锆石U-Pb年龄(143±1Ma,Deng et al., 2013)与铌钽铁矿U-Pb年龄(143±1Ma,Deng et al., 2013);但多数伟晶岩的锆石U-Pb与铌钽铁矿U-Pb法所测得年龄不一致,如阿尔泰3号脉Ⅰ带锆石U-Pb年龄(220±9Ma,Wang et al., 2007)与铌钽铁矿年龄(205.6±2.6Ma,王倩等,2019)、大喀拉苏1号脉锆石U-Pb年龄(270.1±1.7Ma/272.5±1.4Ma,任宝琴等,2011)与铌钽铁矿U-Pb年龄(239.6±3.8Ma,Zhou et al., 2018);(2)白云母的Ar-Ar年龄是否与锆石和铌钽铁矿的U-Pb年龄一致取决于花岗伟晶岩是否存在后期热液活动叠加改造。多数伟晶岩的锆石及铌钽铁矿U-Pb与白云母Ar-Ar法所测得年龄不一致,如可可托海3号脉Ⅱ、Ⅶ带,阿祖拜伟晶岩(邹天人等,1986;王登红等,2000;Wang et al., 2007; 周起凤,2013;Zhang et al., 2016)。广泛的对比研究可以发现白云母Ar-Ar法比锆石、铌钽矿U-Pb法所测得年龄偏年轻,如Gatumba(卢旺达)、阿祖拜、虎斯特、群库尔、Bohemian、Dalan (索马里)、小喀拉苏208号脉伟晶岩(表 7),可能是由于白云母的封闭温度(400±50℃,Dallmeyer and VanBreeman, 1981; Hames and Bowring, 1994; Dunlap, 1997; Ortega-Rivera et al., 1997; Möller et al., 2000; Chakungal et al., 2004; Wang and Li, 2008; Meinhold, 2010)略低于伟晶岩中白云母的形成温度(350 ~ 550℃)所致(Küster, 1995; Glodny et al., 1998; 王登红等,2000;Dewaele et al., 2011; 任宝琴等,2011;Zhang et al., 2016; Zhou et al., 2018),这也可以说明本文的白云母Ar-Ar年龄记录的是最晚期叠加改造热事件时间。
另外,阿尔泰可可托海3号脉年龄数据多样,从外向内Ⅰ~Ⅷ结构带的年龄数据分布范围为160~246Ma (表 7)。从所测各带年龄数据看,不仅分布范围大,而且同一个带年龄有很大差别,如文象伟晶岩带(Ⅰ带)178~246Ma,糖粒状钠长石带(Ⅱ带)180~292Ma。这种年龄值差别一方面可能与20世纪80年代测试水平有关(钟龙等,2011);另一方面,巨型伟晶岩脉形成通常需经历较长时间,样品经受较强热液作用,造成不同程度的氩丢失(钟龙等,2011)。因此,在开展花岗伟晶岩白云母Ar-Ar测年分析时开展岩石结构构造与热液活动分析是必要的。
6 结论(1) 采用不同方法对吐格曼北锂铍矿床进行年代学研究,结果显示:白云母-锡石伟晶岩中锡石U-Pb年龄与含铌钽铁矿-白云母-石英伟晶岩中铌钽铁矿U-Pb年龄分别为468±8.7Ma、464.1±2.7Ma,2件白云母-钠长石-锂辉石伟晶岩样品中锆石U-Pb年龄分别为458.7±2.3Ma、454.7±4.0Ma,1件白云母-钠长石-锂辉石伟晶岩中白云母40Ar/39Ar坪年龄为350.2±1.6Ma。综合分析测试年龄的误差与伟晶岩可能的持续结晶时间,推断吐格曼北锂铍花岗伟晶岩形成于468~454Ma,这表明吐格曼北锂铍矿床成矿作用主要发生在中-晚奥陶世。花岗伟晶岩脉在早石炭世时经历了一次变形与热液叠加改造事件。
(2) 稀有金属花岗伟晶岩中不同矿物记录了不同岩浆-热液阶段的时间,其中锡石年龄代表伟晶岩浆早期结晶阶段的年龄,铌钽铁矿可能为岩浆-热液过渡阶段的产物,蜕晶化的锆石记录的是后期流体作用下锆石U-Pb同位素系统重置的时间,多种方法结果的综合可以更好地约束稀有金属伟晶岩的成矿过程;而白云母Ar-Ar年龄记录的可能是最晚期叠加改造热事件时间。
致谢 野外考察与采样工作中,得到了新疆地矿局第三地质大队刘建兵、张笋、宋俊华工程师等地质同行的支持与帮助;中国地质调查局天津地质调查中心分析实验室涂家润、郝爽、肖志斌老师帮助完成了LA-MC-ICP-MS法锡石同位素测年;两位审稿人对本文的审阅并提出建设性问题及建议,使得本文能更加规范、完整,内容上也更加严谨、充实;在此一并表示衷心的感谢!
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