2021, Vol. 37
2. 自然资源部矿产勘查技术指导中心, 北京 100037;
3. 《中国工程科学》杂志社, 北京 100029;
4. 河北省地矿局第三地质大队, 张家口 075000;
5. 成都理工大学地球科学学院, 成都 610059
2. Mineral Exploration Technical Guidance Center, Ministry of Natural Resources, Beijing 100037, China;
3. Engineering Sciences Press, Beijing 100029, China;
4. The Third Geological Brigade of Hebei Bureau of Geology and Mineral Resources, Zhangjiakou 075000, China;
5. College of Earth Science, Chengdu University of Technology, Chengdu 610059, China
南岭地处早中生代EW向印支期特提斯构造域和晚中生代燕山期NE向太平洋构造域叠置部位，成矿条件优越，是我国重要的金属矿产资源产地，以中生代钨锡矿大爆发而著名，发育有柿竹园、香花岭、瑶岗仙、芙蓉、西华山、大吉山等一大批超大型-大型钨锡多金属矿床，因而长期受到国内外地学界的广泛关注(Hsu, 1943; 徐克勤等, 1982; 韦昌山等, 2004; 华仁民等, 2005; 舒良树等, 2006; 陈骏等, 2014; 袁顺达, 2017; Legros et al., 2020; Xiong et al., 2020)。长期以来，许多学者对该区钨锡矿成矿花岗岩开展了大量的研究工作(徐克勤等, 1982; 黄汲清和陈廷愚, 1986; 裴荣富和毛景文, 1989; 周新民, 2003; 毛景文等, 2004; 王汝成等, 2017)，认为钨锡矿主要与高分异的A型和S型花岗岩有关(蒋少涌等, 2008; 朱金初等, 2008; Jiang et al., 2009; Qiu et al., 2017)。其中，与锡矿有关A型花岗岩广泛分布于钦-杭带与南岭地区交汇部位，具有大量镁铁质包体和较高的岩浆熔融温度，这些特征被认为是幔源岩浆活动的重要证据(Yuan et al., 2019)。但有关钨锡大规模成岩成矿的地球动力学环境，一直没有取得共识，在一定程度上影响着新一轮地质与找矿工作的方向与思路(周新民, 2003; Mao et al., 2018)。
湖南大义山锡矿位于南岭成矿带和钦-杭成矿带(简称钦-杭带)的交汇部位，是南岭地区重要的锡多金属矿集区。经过多年的地质找矿工作，已发现狮形岭、狮茅冲、白沙子岭等一大批中型及以上锡多金属矿床(伍光英等, 2005)，取得了重要找矿进展(曾钦旺等, 2016)。前人对大义山地区与花岗岩有关锡多金属矿床开展了广泛的研究工作，主要包括区域成矿规律(伍光英等, 2005)、成矿地质特征与控矿要素(周厚祥等, 2005; 曾志方, 2013)、矿床成因(刘铁生, 2002)、成矿动力学背景(孔华等, 2014)、成矿花岗岩成因和侵位就位机制(费利东等, 2012)、成矿年代学(孔华等, 2014; 张晓军等, 2014; Sun et al., 2018; Zhang et al., 2021)、深部找矿预测(吴迎春等, 2008; 贺文华, 2011; 曾钦旺等, 2016)以及找矿方向探索(李惠纯, 2000)等。野外调查发现，大义山地区锡矿成矿花岗岩和锡矿化广泛发育电气石，具有明显的富硼特征，与南岭地区多数锡矿富氟的特征存在一定差别(袁顺达, 2017)。目前，关于大义山锡矿成矿花岗岩的成因类型及动力学背景仍缺乏系统的研究。本文拟通过对大义山地区锡矿成矿花岗岩系统的主量元素、微量元素和Sr-Nd-Hf同位素组成研究，厘定花岗岩的成因，探讨其形成的动力学背景，为深入理解该区复杂的成岩成矿作用提供重要的科学依据。
1 区域地质背景湖南大义山锡矿位于南岭成矿带和钦-杭带的交汇部位，邻区发育有一大批超大型-大型钨锡多金属矿床(图 1)。区内除缺失志留纪、古近-新近纪地层外，其他地层围绕大义山岩体周边多有分布(图 2)。震旦系-寒武系主要为一套浅海相类复理石沉积建造，出露于大义山岩体西南。震旦系岩性以石英砂岩夹砂质板岩、板岩、长石石英砂岩为主；寒武系岩性以浅变质砂岩类为主，夹杂泥质及粉砂质板岩类。晚古生界为陆缘海浅海相碳酸盐沉积为特征；其中泥盆系主要为中厚层石英砂岩、砂岩、粉砂岩以及中厚层至厚层灰岩、白云质灰岩；石炭系主要为中厚层灰岩、白云岩以及石英砂岩、粉砂岩、页岩等；二叠系岩性主要为中厚层灰岩、含铁锰硅质岩、硅质页岩以及石英砂岩、粉砂岩。泥盆、石炭系碳酸盐岩与岩体接触部位往往形成矽卡岩型锡多金属矿，另外岩体周边河谷多赋存有砂锡矿(曾志方, 2013)。
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图 1 南岭地区构造位置图(a)和华南中生代花岗质侵入岩及主要钨锡矿床分布图(b)(据Sun et al., 2018) Fig. 1 Simplified tectonic map of Nanling Range (a) and the distribution of granitoids and W-Sn deposits in this area (b) (after Sun et al., 2018) |
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图 2 大义山锡矿地质简图(据Sun et al., 2018) Fig. 2 The simplified tectonic map of the Dayishan Sn deposit (after Sun et al., 2018) |
大义山地区经历了多期构造活动，形成了以断裂为主、褶皱次之的构造格局(张晓军等, 2014)。阳明山-塔山岩体东西向构造带与大义山岩体北西向构造带形成该区域的主干构造，其中“大义山式”北西向张扭性断裂构造具有继承性发展的特征，控制了大义山花岗岩体的侵入活动(曾钦旺等, 2016)。基底层褶皱-泗洲山复背斜呈北北东向展布，其余褶皱轴向多呈近南北向-北北西向展布，紧靠岩体部位多被断层所破坏(伍光英等, 2005)。
大义山花岗岩体为燕山期花岗岩，受北西向邵阳-郴州基底断裂严格控制，沿北西向构造带多期次侵位，平面上呈扁长椭圆状，长轴走向北西(NW 325°)，呈长条状侵入于印支期构造层之中。按侵入期次，该岩体可分为三期，分别为早侏罗世中-细粒斑状(含角闪石)黑云钾长花岗岩、中侏罗世中粗-细(微)粒斑状黑云二长花岗岩及细粒(少斑)二云二长花岗岩、晚侏罗世中细-细(微)粒二长花岗岩。区内与大义山岩体有关矿化以锡矿为主，铜矿、铅锌矿次之，主要有蚀变花岗岩型、云英岩脉型、石英脉型、矽卡岩型等，并在岩体外围有大量砂锡矿分布(张晓军等, 2014)。Sun et al. (2018)通过蚀变花岗岩型锡矿、云英岩脉型锡矿锡石U-Pb年龄、成矿黑云母二长花岗岩锆石U-Pb年龄及晚期含辉钼矿石英脉中辉钼矿Re-Os年龄精确限定了大义山锡矿猫仔山矿区锡矿成矿年龄为~156Ma。Zhang et al. (2021)通过对大义山藤山坳矿区锡石及成矿花岗岩U-Pb测年和白云母40Ar-39Ar测年，也获得了相近的结果。
2 岩石特征本次研究样品全部为猫仔山矿区坑道样品，为似斑状黑云母二长花岗岩，其成岩年龄为~156Ma (Sun et al., 2018)。花岗岩具似斑状结构，块状构造。主要成分为石英、斜长石、钾长石和少量黑云母。钾长石为自形-半自形板状，可见卡巴斯双晶，部分蚀变为绢云母，粒径为0.2~0.4cm，含量约34%；石英为他形粒状，具明显的溶蚀结构，粒径0.1~0.5cm，含量为30%左右；斜长石为半自形板状-他形粒状，粒径为0.1~0.3cm，含量为30%左右；黑云母为半自形鳞片状，粒径0.3~0.2mm，含量5%左右，局部可见电气石“囊包”(图 3)。
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图 3 大义山锡矿成矿花岗岩及矿石典型样品照片 (a)含电气石囊包黑云母二长花岗岩；(b)贫矿含电气石石英脉；(c)含锡石电气石-石英脉；(d)港湾状石英斑晶(正交偏光)；(e)巨斑状黑云母二长花岗岩与似斑状黑云母二长花岗岩接触界线附近发育大量针状电气石(单偏光)；(f)电气石囊包中粒状电气石(单偏光) Fig. 3 The samples of metallogenic granite and typical ore in the Dayishan Sn deposit (a) biotite monzogranite bearing tourmaline nodule; (b) barren quartz-tourmaline vein; (c) quartz-tourmaline vein bearing cassiterite; (d) dissolved quartz in porphyry biotite monzogranite (CPL); (e) tourmaline needles in the margin area of biotite monzogranite (PPL); (f) tourmaline grains in the tourmaline nodule (PPL) |
全岩主量元素分析在澳实分析检测(广州)有限公司完成，检测仪器为X荧光光谱仪。按要求制备的定量样品煅烧后加入Li2B4O7-LiBO2助熔物，充分混和后，放置在自动熔炼仪中，使之在1000℃以上熔融；熔融物倒出后形成扁平玻璃片，再用X射线荧光光谱分析。本方法分析的结果以氧化物表示，分析精度优于5%。
3.2 微量、稀土元素分析微量及稀土元素分析在中国科学院地球化学研究所矿床地球化学国家重点实验室完成，分析仪器均为电感耦合等离子体质谱仪(ICP-MS)，分析精度优于5%。样品处理过程如下：准确称取50mg样品(200目)放入装有洗净的聚四氟乙烯塑料溶样罐的不锈钢衬套中，加入1mL HF，在电热板上蒸干以去掉大部份SiO2，再加入1mL HF和0.5mL HNO3，盖上盖子拧紧，在烘箱中于200℃分解40小时，取出冷却后，于电热板上低温蒸干，加入1mL HNO3再蒸干，重复一次；最后加入2mL HNO3和5mL蒸馏水，重新盖上盖子密封，于130℃溶解残渣3小时，再取出，冷却后加入500ng Rh内标溶液，转移至50mL离心管中上机测试，具体分析过程参见Qi and Grégoire (2000)。
3.3 全岩Sr-Nd同位素全岩Sr-Nd同位素分析在天津地质调查中心实验测试室采用TRITON热电离质谱测定。测试前，首先取200目的岩石粉末样，烘干后完全溶解于HF+HClO4+HNO3的混合酸中，用AG50W×12强酸性阳离子交换树脂分离Rb、Sr，然后用HEHEHP树脂(P507)技术分离纯化Nd。采用阳离子交换树脂分离提纯出Sr和Nd。Sr、Nd同位素比值分别采用86Sr/88Sr=0.1194、146Nd/144Nd=0.7219进行质量分馏校正。87Rb/86Sr和147Sm/144Nd比值用全岩Rb、Sr、Sm和Nd含量计算，λRb-Sr=1.42×10-12a-1；Sm-Nd同位素计算过程中，球粒陨石值、亏损地幔值和大陆地壳平均值的计算参数分别为：(143Nd/144Nd)DM=0.51315，(147Sm/144Nd)DM=0.21360，(147Sm/144Nd)cc=0.11800；λSm-Nd=6.54×10-12a-1。
3.4 锆石Hf同位素锆石分选在首钢地质勘查院进行。机械性粉碎含有锆石的岩石样品至80目，重力磁力分选后利用双目镜把锆石颗粒挑出。挑选出的锆石样品在北京锆年领航科技有限公司完成制靶和阴极发光照相。在双目镜下，选择透明、无包裹体、无裂隙、晶型好、颗粒较大的锆石单矿物粘在双面胶上，利用无色透明的环氧树脂固定，待环氧树脂固化后，将锆石抛光，使其内部结构剖面充分暴露。制靶完毕后，对样品进行阴极发光图像(CL)的采集，以便观察锆石的内部结构，帮助选择适宜的测试点位。单颗粒锆石的激光剥蚀等离子体质谱(LA-ICP-MS)原位测试锆石U-Pb同位素完成后，选择对应年龄分析位置，在中国地质大学(武汉)地质过程与矿产资源国家重点实验室对所测试锆石进行原位Hf同位素分析。实验在多接收等离子体质谱仪(MC-ICP-MS)上进行。激光束直径为44μm，剥蚀频率为8Hz，每8个测点添加1个91500标样进行控制，详细的仪器操作条件和数据处理方法见(Hu et al., 2012)。
4 分析结果 4.1 主量元素特征黑云母二长花岗岩主量元素具有相对富SiO2(73.58%~74.76%)、Al2O3(13.67%~14.00%)、Na2O(3.65%~3.90%)、K2O(3.49%~4.24%)，贫Fe2O3T(1.18%~2.18%)、MgO(0.04%~0.06%)、CaO(0.54%~0.59%)、P2O5(0.04%~0.06%)的特点(表 1)。全碱含量较高，Na2O+K2O为7.30%~8.03%，平均为7.76%；K2O/Na2O值为0.92~1.12。在TAS分类图解中，样品落入亚碱性花岗岩区域(图 4a)；A/CNK值为1.15~1.26，A/NK值为1.26~1.39，在A/NK-A/CNK分类图解中，落入过铝质范围内(图 4b)；SiO2-K2O图解显示岩石具有高钾钙碱性的特征(图 4c)。
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表 1 湖南大义山锡矿黑云母二长花岗岩主量元素(wt%)和微量元素(×10-6)分析结果 Table 1 Major (wt%) and trace elements (×10-6) of biotite monzonite in the Dayishan tin deposit |
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图 4 大义山黑云母二长花岗岩主量元素地球化学判别图 (a)全碱-硅图解(Middlemost, 1985)；(b)A/NK-A/CNK判别图(Peccerillo and Taylor, 1976)；(c) SiO2-K2O图解(Rickwood, 1989) Fig. 4 TAS (a, after Middlemost, 1985), A/NK vs. A/CNK (b, after Peccerillo and Taylor, 1976) and K2O vs. SiO2 (c, after Rickwood, 1989) diagrams of the Dayishan biotite monzonite |
花岗岩样品稀土元素总量较低(126×10-6~147×10-6)，LREE/HREE比值为3.17~3.44，(La/Yb)N为2.23~2.59，δEu值为0.06~0.07 (表 1)。在球粒陨石标准化稀土元素配分图解中，样品表现出相对富集轻稀土元素、贫重稀土元素的特点，但轻、重稀土元素分馏不明显，稀土元素配分曲线为缓右倾的“V”型，具有强烈的Eu负异常(图 5a)。在微原始地幔标准化量元素蛛网图中，样品富集Rb、Th、U、Ta和Nd等元素，亏损Ba、Nb、Sr、Eu等元素(图 5b)。
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图 5 大义山锡矿黑云母二长花岗岩球粒陨石标准化稀土元素配分图解(a)和原始地幔标准化微量元素蛛网图(b)(标准化数值据Sun and McDonough, 1989) 数据来自Li et al. (2007b)、Yao et al.(2014)、章荣清等(2016)、Zhang et al.(2017) Fig. 5 Chondrite-normalized REE patterns (a) and primitive mantle-normalized trace element spider diagrams (b) of the Dayishan biotite monzonite (normalization values after Sun and McDonough, 1989) The data are referenced from Li et al. (2007b), Yao et al. (2014), Zhang et al.(2016, 2017) |
本次共对3件样品进行了Sr-Nd同位素分析，数据列于表 2。87Rb/86Sr初始比值变化范围较大(0.7743~0.8212)。由于异常高的Rb/Sr和87Sr/86Sr比值，年龄校正后的Sr同位素组成具有较大的不确定性，因此初始的87Sr/86Sr比值不能用于岩石成因讨论。分析样品的fSm/Nd范围为-0.09~-0.05，在有效范围内(-0.2~0.4，Wu et al., 2000)。3件样品均具有亏损的Nd同位素组成，(143Nd/144Nd)i范围为0.512174~0.512298，εNd(t)值均为负值(-5.1~-2.7)，二阶段模式年龄较集中(1.2~1.4Ga)。
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表 2 湖南大义山锡矿黑云母二长花岗岩Sr-Nd同位素分析结果 Table 2 Sr and Nd isotopic compositions of biotite monzonite in the Dayishan tin deposit |
MC-29锆石样品Hf同位素分析结果(表 3，锆石年龄据Sun et al., 2018)显示，锆石初始(176Hf/177Hf)i值为0.282476~0.282536，fLu/Hf值为-0.98~-0.92，显示出较为均一的特征。计算得出的εHf(t)值为-7.03~-4.93，二阶段Hf模式年龄值为1.5~1.6Ga。
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表 3 湖南大义山锡矿黑云母二长花岗岩锆石Hf同位素分析结果 Table 3 Zircon Hf isotopic compositions of biotite monzonite in the Dayishan tin deposit |
大义山黑云母二长花岗岩具有较高的SiO2(73.58%~74.76%)含量、FeOT/(FeOT+MgO)比值(0.95~0.97)、FeOT/MgO比值(18.75~32.69)、10000×Ga/Al比值(3.48~4.08)和较低的CaO (0.54%~0.59%)、P2O5(0.04%~0.06%)、MgO (0.04%~0.06%)、TiO2(0.04%~0.06%)、Ba (68.40×10-6~77.10×10-6)、Sr (16.60×10-6~20.00×10-6)含量(表 1)以及平坦的稀土元素配分曲线(图 5a)。这些特征均与A型花岗岩相似，与华南钨锡成矿花岗岩特征相近(Whalen et al., 1987; 郭春丽等, 2013; Zheng et al., 2017a, b)。其较高的Rb元素含量和Rb/Sr、Rb/Ba比值，较低的Ba、Sr、P、Nb、Ti等元素含量及CaO/(Na2O+K2O)(0.07~0.08)、Zr/Hf (19~22)和Nb/Ta (2.34~2.56)比值，以及强烈的Eu负异常特点，也显示出高度结晶分异的特点。一般认为，当A型花岗岩受到结晶分异作用影响时，会与S型花岗岩和高分异的I型花岗岩具有相似的地球化学特征(Chappell and White, 1992; King et al., 1997)。本文分析的所有岩石样品的SiO2含量均高于73.00%，A/CNK值在1.15~1.26之间，变化范围较小，平均为1.20，均为过铝质岩石(图 4b)，似乎也与S型花岗岩相似。然而，其较低的P2O5(0.04%~0.06%)含量和较高的Na2O(3.65%~3.90%)含量却与S型花岗岩明显不同(King et al., 1997)。另外，尽管黑云母二长花岗岩具有较高的A/CNK (1.15~1.26)比值，但A型和I型花岗岩也可以具有弱的过铝质特征(King et al., 1997)。因此，可基本排除S型花岗岩的可能性。
锆石饱和温度计算结果显示(Watson and Harrison, 1983)，大义山锡矿黑云母二长花岗岩浆温度的估算结果仅为716~725℃(表 1)。这与本文黑云母二长花岗岩存在显著的结晶分异特征一致。因为岩浆中锆石和褐帘石的结晶分异会造成岩A型和I型花岗岩中Zr含量的降低(King et al., 1997)，因此，岩浆的实际温度应高于上述估算值。这一特征与铝质A型花岗岩产于高温岩浆(>760℃)相似(King et al., 1997)。此外，成矿花岗岩10000Ga/Al值在3.48~4.08之间，平均值为3.73，明显高于世界I和S型花岗，而与A型花岗岩3.75的比值接近(肖庆辉等, 2009)。在10000Ga/Al-Zr图解中，所有黑云母二长花岗岩样品全部落于A型花岗岩的区域(图 6a)。值得注意的是，对于高分异花岗岩，其元素含量指标的图解可能失效，因此高分异的A型和I型花岗岩的判别应予以慎重。
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图 6 大义山黑云母二长花岗岩岩石类型判别图解 (a)A、I、S型花岗岩10000 Ga/Al-Zr判别图解(Whalen et al., 1987)；(b)A型花岗岩SiO2-FeOT/(FeOT+MgO) 判别图解(Whalen et al., 1987)；(c)A、I、S型花岗岩SiO2-FeOT/MgO判别图解(Frost et al., 2001)；(d)A型花岗岩的A1亚类和A2亚类判别图(Eby, 1990) Fig. 6 Discrimination diagrams for the Dayishan mineralized biotite monzonite (a) 10000 Ga/Al vs. Zr diagram (Whalen et al., 1987); (b) SiO2 vs. FeOT/(FeOT+MgO) diagram (Whalen et al., 1987); (c) SiO2 vs. FeOT/MgO) diagram (Frost et al., 2001); (d) Y/Nb vs. Rb/Nb diagram (Eby, 1990) |
研究表明，相对于高分异的I型花岗岩，A型花岗岩具有相对较高的FeOT/MgO和FeOT/(FeOT+MgO)比值，是判别花岗岩类型的重要指标(Whalen et al., 1987; Frost et al., 2001)。本次研究的黑云母二长花岗岩具有较高的FeOT/MgO(18.75~32.69)比值和FeOT/(FeOT+MgO)(0.95~0.97)比值，表明本文研究黑云母二长花岗岩为A型花岗岩(图 6b，c)。此外，Eby (1992)根据A型花岗岩产出环境不同，将A型花岗岩划分为A1和A2型，其中，A1花岗岩形成于非造山环境，而A2花岗岩形成于陆陆碰撞或弧环境。图 6d显示，本文研究黑云母二长花岗岩样品全部落在A2型花岗岩区域，属于高分异A2型花岗岩。
值得注意的是，大义山地区恰好位于扬子、华夏两大古陆块拼贴形成的钦-杭古板块结合带和南岭成矿带的交汇部位。前人研究发现，钦-杭带的湘南-桂北地区存在一条呈北北东向展布的高εNd(t)值(>-8)和低tDM模式年龄值(< 1.5Ga)的花岗岩带，包括花山、姑婆山、骑田岭、锡田等花岗岩岩基和岩株，这些花岗岩的形成时代集中在150~165Ma，具有A型花岗岩特征，并有大量钨锡矿床伴生，被认为是一条特征独特的铝质A型花岗岩带(蒋少涌等, 2008; 朱金初等, 2008; 周云等, 2013; 陈骏等, 2014)。可见，大义山黑云母二长花岗岩可能为北东向A型锡矿花岗岩带的一部分。
5.2 岩石成因作为钦-杭带北北东向A型花岗岩的一部分(朱金初等, 2008; 赵葵东等, 2009; 王禄彬等, 2011; 周永章等, 2017)，大义山成锡矿花岗岩具有相对较负的εNd(t)值(-5.1~-2.7)和年轻的Nd模式年龄(1.2~1.4Ga)，以及较负的εHf(t)值(-7.03~-4.93)和年轻的Hf模式年龄(1.5~1.6Ga)，与南岭地区成锡矿花岗岩及钦-杭带A型花岗岩同位素组成基本一致(图 7、图 8)(Gilder et al., 1996; 陈骏等, 2014)。洪大卫等(2002)认为该高εNd(t)值、低Nd模式年龄花岗岩带可能是地幔物质上涌加入地壳的一条重要通道，导致花岗岩的εNd(t)值升高和Nd模式年龄值降低。另外，对白沙子岭锡矿云英岩脉型锡矿中石英流体包裹体Rb和Sr同位素研究表明，其初始Sr同位素值为0.70679，与壳幔边界地区Sr初始值0.707近乎一致，也暗示石英流体包裹体中的成矿热液除了壳源物质外，还可能有地幔物质的混入(张晓军等, 2014)。邻区芙蓉锡矿床中成矿流体的稀有气体同位素3He/4He测定值为0.14~2.95Ra，也具有壳、幔混合的特点(李兆丽等, 2006; 单强等, 2014)。
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图 7 大义山及南岭地区主要钨锡矿床成矿花岗岩全岩εNd(t)-t相关图解 数据来源：黄沙坪矿床成矿花岗岩(Hu et al., 2017)、荷花坪成矿花岗岩(蔡明海等, 2013; 王显彬等, 2013; 章荣清等, 2016)、香花岭花岗岩(邱瑞照等, 2003)、锡田花岗岩(Zhou et al., 2015)和本文；华南元古代地壳(Shen et al., 1996) Fig. 7 Plot of intrusive age t vs. εNd(t) for the mineralized granites in the Dayishan Sn deposit Data sources: mineralized granites are sourced from Huangshaping granite (Hu et al., 2017), Hehuaping granite (Cai et al., 2013; Wang et al., 2013; Zhang et al., 2016), Xianghualing granite (Qiu et al., 2003), Xitian granite (Zhou et al., 2015) and Dayishan granite of this work; The Proterozoic crustal data of South China (Shen et al., 1996) |
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图 8 湖南大义山锡矿成矿花岗岩锆石Hf同位素εHf(t)-锆石年龄图 南岭地区锡矿花岗岩和华夏板块基底岩石Hf同位素数据据Liu et al. (2017)及所引用文献 Fig. 8 Plot of intrusive age t vs. εHf(t) for the mineralized granites in the Dayishan Sn deposit The data of tin mineralized granite and Hf isotope data of Cathaysia block basement from Nanling area from Liu et al., 2017 and references therein |
如上文所述，大义山锡矿黑云母二长花岗岩母岩浆经历了显著的结晶分异作用。其Ba、Sr、Eu的亏损指示了斜长石、钾长石的分离结晶，Nb、Ti的亏损指示了富钛铁矿物(钛铁矿、金红石)的分离结晶。值得注意的是，大义山锡矿成矿花岗岩轻、重稀土配分呈“V”型展布特征，具有明显的四分组效应(图 5a)。据研究，具有稀土元素四分组效应的花岗岩几乎全都是岩浆作用晚阶段残余熔体的产物(赵振华等, 1999; Peretyazhko and Savina, 2010)。强烈的结晶分异会使挥发分在残余熔体中富集，为流体-熔体相互作用提供物质基础。富挥发分的流体对熔体中的稀土元素具有很大的萃取能力，影响稀土元素在熔体和流体之间的分配，使得残余熔体形成稀土元素四分组效应(赵振华等, 1999)。稀土元素四分组效应的存在，表明该花岗岩在地壳深部部分熔融形成初始岩浆之后，岩浆上升侵位过程中经历了高度的结晶分异，进而形成了富挥发分的流体和熔体共存的体系，并经历了与流体的相互作用。
研究表明，四分组效应仅见于高度演化且富H2O、CO2、Li、B、Cl、F等元素的火成岩中，为与热液发生强烈相互作用的晚期岩浆分异产物(薛怀民等, 2009)。这与大义山成矿花岗岩中常见的“电气石”囊包及石英溶蚀现象一致(图 3a，d，f)。这种囊包多具双层结构，即内部黑色内核(主要由电气石、石英以及少量微斜长石和钠长石组成)和外部淡色环晕(为富含石英而不含黑云母的淡色花岗岩)(Sinclair and Richardson, 1992; Trumbull et al., 2008; Drivenes et al., 2015)。此结构在一些富硼成锡矿花岗岩体系中较为常见，如玻利维亚锡矿省(Lehmann et al., 1990)、英格兰西南部锡矿省(Drivenes et al., 2015)、东南亚锡矿省、内蒙古大兴安岭西南段磨盘山锡矿(Duan et al., 2020)、云南云龙锡矿(Yu and Jiang, 2003)以及桂北锡多金属矿集区(Zhao et al., 2019)，是岩浆-热液过渡态的一种表现形式(Yang and Jiang, 2012; Lira and Poklepovic, 2017; Duan et al., 2020; Hong et al., 2020; 郭佳等, 2020)。花岗质岩浆中较高的硼含量可以较大程度降低岩浆的结晶温度，提升岩浆中水的溶解度，促进岩浆的结晶分异，有利于锡在岩浆中的富集，提升岩浆的锡成矿能力(Pollard et al., 1987)。大义山锡矿广泛发育的电气石化蚀变，指示成锡花岗岩具有富挥发分硼的特征。综上表明大义山富硼的成锡花岗岩源于壳源岩浆和幔源岩浆的混合，并经历了强烈的结晶分异和流体出溶作用。
5.3 构造环境前文研究表明，大义山锡矿成矿花岗岩为A2型花岗岩(图 6d)。一般认为，A2型花岗岩形成于各种类型的伸展环境中，从大陆弧或弧后到碰撞后以及板内都可以形成(Whalen et al., 1987; Eby, 1992; Förster et al., 1997)。在构造环境判别图解上(图 9)，大义山锡矿成矿花岗岩全部落在后碰撞花岗岩和板内花岗岩区域的重叠部分，这一特征与南岭地区成钨锡花岗岩一致(图 9)，指示花岗岩形成于伸展构造背景。大义山岩体内部流动构造不发育，接触带泥盆系-石炭系围岩形态基本上保持了原状，岩浆呈“被动”侵位的特征，也证实了这一认识(伍光英等, 2000)。另外，南岭地区在燕山早期存在碱性玄武岩(177~178Ma)、双峰式火山岩(158~179Ma)和A型花岗岩(176~178Ma)岩石组合，也暗示了华南自燕山早期就开始处于伸展的构造环境(赵振华等, 2000; 陈培荣等, 2002; Ye et al., 2013)。宁远地区玄武岩地幔包体元素地球化学和Re-Os同位素也说明，华南中生代存在岩石圈减薄过程(Liu et al., 2012)。随后该区强烈的花岗质岩浆活动亦与这种岩石圈伸展裂解作用密切相关(Gilder et al., 1996)。
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图 9 湖南大义山锡矿成矿花岗岩Nb+Y-Rb(a)和Y-Nb构造环境判别图解(b)(据Pearce, 1996) 南岭地区钨锡矿成矿花岗岩数据引自Zhang et al. (2017)、Li et al. (2007a)、Yao et al. (2014)、Hu et al. (2017)和章荣清等(2016). Syn-COLG-同碰撞花岗岩；WPG-板内花岗岩；ORG-洋中脊花岗岩；VAG+S-COLG-碰撞和火山弧花岗岩；VAG-火山弧花岗岩；Post-COLG-碰撞后花岗岩 Fig. 9 Discrimination diagrams of Nb+Y vs. Rb (a) and Y vs. Nb (b) for the Dayishan mineralized biotite monzonite (after Pearce, 1996) 南岭地区钨锡矿成矿花岗岩数据引自Zhang et al. (2017)、Li et al. (2007a)、Yao et al. (2014)、Hu et al. (2017)和章荣清等(2016). Syn-COLG-同碰撞花岗岩; WPG-板内花岗岩; ORG-洋中脊花岗岩; VAG+S-COLG-碰撞和火山弧花岗岩; VAG-火山弧花岗岩; Post-COLG-碰撞后花岗岩 |
在中-晚朱罗世伸展背景下，南岭地区不仅形成了大量钨锡矿床，相近成矿年龄的斑岩型铜矿也屡见不鲜，如湘南地区的铜山岭铜铅锌矿(161Ma；Zhao et al., 2016)和宝山铜铅锌矿(158Ma；Zhao et al., 2017)。统计发现，南岭地区中-晚朱罗世铜铅锌矿虽与钨锡矿位置有重叠，却形成稍早(黄旭栋等, 2017)，而且两期岩浆活动具有完全不同的地球化学特征，铜铅锌多金属矿床成矿斑岩具有较高的氧逸度、低初始ISr比值、高Cl、低F等特点，明显的幔源特征，而该区钨锡矿成矿花岗岩则不同，以低氧逸度、高度分异、低的εNd(t)值为特征(Ding et al., 2015及本文)，说明早期铜多金属矿形成时成矿花岗岩存在受俯冲板片流体交代的幔源物质组分加入，而钨锡成矿则不存在俯冲板片来源物质组分参与(Liu et al., 2012及作者未发表的电气石硼同位素数据)。另外，沿着中国东部东南沿海越来越多的侏罗纪斑岩-矽卡岩铜多金属矿床逐渐被发现，表明存在一个中晚侏罗世的大陆岩浆弧和相关的斑岩-矽卡岩铜矿带，如德兴、永平、古田、岭后、旗鼓岭、陂头面、龙头岗、新寮岽等铜多金属矿(王小雨等，2016; Mao et al., 2017; 郑伟等, 2018a, b)，指示170Ma左右Izanagi板块或古太平洋板块开始向欧亚大陆发生斜向俯冲，中国东部大陆边缘成为活动大陆边缘(Mao et al., 2021)。
近年来，岩浆岩、构造、矿床等多方面的证据也表明，华南在180~170Ma已经完成由特提斯构造域向滨太平洋构造域的转换(董树文等, 2007; 张岳桥等, 2012)。对于钦-杭成矿带，其北北东向的走向完全不同于近东西走向的印支碰撞带，而与古太平洋板块的俯冲缝合线走向一致，华仁民等(2005)、蒋少涌等(2008)和毛景文等(2018)也认为，约160Ma的华南内部拉张事件可能与古太平洋板块的俯冲消减有关，而不是后碰撞或后造山伸展减薄所致。160~150Ma，伴随着俯冲板片的后撤，俯冲板片开天窗或撕裂，软流圈物质上涌到下地壳形成壳幔源型花岗质岩浆，岩浆的分异与演化，形成了南岭大规模钨锡成矿事件(毛景文等, 2011)。因此，本文认为，~156Ma左右，Izanagi俯冲板块开天窗或撕裂，导致软流圈物质上涌到下地壳，形成了壳幔源混合型花岗质岩浆。其较高的硼含量促使岩浆经历了强烈的结晶分异，有助于岩浆演化晚期岩浆热液的出溶和锡矿化的形成。
6 结论本文对湖南大义山成锡矿黑云母二长花岗岩开展了详细的岩石学、Sr-Nd-Hf同位素和全岩主量、微量元素分析，在结合大量前人分析结果的基础上，得出如下结论：
(1) 成矿花岗岩具有较高的SiO2含量和FeOT/(FeOT+MgO)比值、FeOT/MgO比值、A/CNK比值、10000×Ga/Al比值，较低的CaO、P2O5、MgO、TiO2、Ba、Sr含量，以及较低的锆石饱和温度，这些特征均与A型花岗岩相似，属高分异的A2型花岗岩。
(2) 成矿花岗岩具有富挥发分硼的特征，Sr-Nd-Hf同位素指示大义山富硼成锡花岗岩源于壳源岩浆和幔源岩浆的混合，并经历了强烈的结晶分异和流体出溶作用。
(3) 成矿花岗岩的形成与Izanagi俯冲板块开天窗或撕裂有关。在此背景下，软流圈物质上涌到下地壳，形成了壳幔源混合型花岗质岩浆，其较高的硼含量促使岩浆经历了高度的结晶分异，有利于晚期锡矿的形成。
致谢 湖南四一八地质队陈文辉、宁勇云、毛红光在野外工作中给予了帮助与支持；中国地质科学院矿产资源研究所武广研究员、中国地质大学(北京)张德会教授及两位审稿人对本文修改提出了宝贵建议；在此一并深表谢意。
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