Geochemical characteristics and geochronology of porphyroid biotite monzogranite from the Reshui Mo polymetallic deposit, East Kunlun Mountains
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摘要:
热水钼矿区处于东昆仑造山带东段，大地构造位置位于北昆仑岩浆弧，区内侵入岩较发育，其中与热水钼多金属矿密切相关的矿化似斑状黑云母二长花岗岩岩相学及地球化学数据显示，SiO2含量在67.64%～71.09%，铝饱和指数（A/CNK）为0.86～1.11，为准铝质到过铝质，K2O/Na2O值1.35～2.32，里特曼指数为1.73～1.99，属于高钾钙碱性I型花岗岩。岩石总体上富集大离子亲石元素Rb、Th、U、K、Pb等，明显亏损高场强元素Ta、Nb、Ce等，贫P、Ti。稀土元素总量（ΣREE）为94.27×10-6～127.44×10-6，平均为110.92×10-6，稀土元素配分曲线呈右倾型，具有较明显的轻稀土富集、重稀土亏损的特征，弱到中等程度的负铕异常。LA-ICP-MS锆石U-Pb年龄为（230.9±1.4）Ma，形成于印支期，钼多金属矿与这一时期岩浆活动密切相关。综合分析表明，似斑状黑云母二长花岗岩形成构造体制转换阶段，在热水地区具有寻找斑岩型矿床潜力。
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关键词:
- 似斑状黑云母二长花岗岩 /
- 地球化学 /
- 锆石U-Pb定年 /
- 热水钼矿区
Abstract:The Reshui Mo polymetallic deposit is located at the North Kunlun magmatic arc, where lots of intrusive rocks occur. Geochemical data reveal that the porphyroid biotite monzogranite from East Kunlun is rich in silicon (67.64%-71.09%), Al2O3 (13.8%-14.57%), Na2O(2.23%-3.02%), and K2O(3.95%-5.18%), with ratios of K2O/Na2O being 1.35-2.32 and A/CNK being 0.86-1.11, 1.01 on average, suggesting that the granite should belong to high potassic calc-alkaline and I type granite. The porphyroid biotite monzogranite is intensively depleted in HFSE (Ta, Nb, mCe), enriched in LILE (Rb, Th, U, K, Pb), and poor in P, Ti. The total rare earth elements (ΣREE) are 94.27×10-6-127.44×10-6, with an average of 110.92×10-6. The rare earth element distribution curve shows the right-inclined type, and has characteristics of obvious enrichment of light rare earth and depletion of heavy rare earth elements. LA-ICP-MS zircon U-Pb dating shows that the formation age of the rock is (230.9±1.4) Ma, belonging to Indosinian stage. The molybdenum polymetallic deposit is closely related to the magmatic activity during this period. Based on tectonic history and the structure environment in combination with the geochemical characteristics, the authors hold that the porphyritic biotite monzonitic granite of the Reshui deposit was formed at the structural transformation stage, and Rershui area has potential for finding porphyry deposits.
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1. 前言
太行山存在重力梯度带是华北克拉通最显著的地质特征之一，该梯度带两侧的地貌、大地热流值、地壳厚度和岩石圈厚度存在明显的差异，造成这种差异的原因是华北岩石圈减薄存在时空不均一性[1]。沿该重力梯度带北东向发育大量的晚中生代侵入-火山岩带，特别是在太行山北段。前人对这些侵入岩开展了大量的年代学和地球化学研究[2-3]，取得了重要进展。同时在太行山中北段探明存在多个中小型矽卡岩铜多金属矿[4-5]和石湖大型金矿床[6]。近几年在该地区新探明了木吉村大型斑岩型铜(钼)矿[7]和安妥岭大型斑岩型钼矿[8]，暗示太行山北段具有很大的找矿潜力。区域地质工作显示，赤瓦屋岩体是太行山北段南部典型的杂岩体[9]，前人虽然对该岩体开展过一些锆石测年工作，但多限于岩体边缘相石英闪长岩的研究[10-13]，最近的找矿工作新类型铜钨矿体主要集中于岩体中心相斑状花岗闪长岩。因此，本文对赤瓦屋岩体不同岩相开展详细的锆石U-Pb 测年工作，结合区域含矿岩体的年代学资料，以期对太行山北段中生代金属矿床的成矿规律有更明确的认识。
2. 区域地质
研究表明，太行山北段的构造演化大致经历了3 个主要阶段，分别为太古宙变质基底形成阶段、元古宙至古生代稳定发展阶段和中生代活化阶段[14]。阜平杂岩是华北克拉通太古宙变质结晶基底的一部分，现今表现为NE向展布的穹隆状构造，主要岩性为黑云斜长片麻岩、角闪斜长片麻岩、浅粒岩夹斜长角闪岩,该套岩石地层单元普遍遭受强烈区域变质及混合岩化作用[15]。除了阜平杂岩以外，还发育一系列元古宙—侏罗纪沉积地层。岩浆岩是太行山北段中生代活化阶段的产物，沿太行山重力梯度带呈NNE向展布（图 1-a），其分布受东、西两侧分布的NNE 向紫荆关断裂和乌龙沟断裂带控制[5]，由NNE向分布的多个岩基（体）和髫髻山组火山岩组成，由北向南依次发育大河南、王安镇岩基和麻棚、赤瓦屋岩体（图 1-b），这些岩体为中酸性高钾钙碱性花岗质岩石[2]。其中王安镇岩基周缘探明了多个斑岩-矽卡岩型多金属矿床，新发现的木吉村大型斑岩铜钼矿和安妥岭大型斑岩型钼矿分别位于该岩基的南缘和北缘；在麻棚岩体西侧1~4 km探明了太行山地区最大的金矿——石湖金矿（图 1-b）。
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赤瓦屋岩体位于太行山北段北东向岩浆带的南端，该岩体平面上呈近圆状,直径约5 km，面积约63 km2。根据前人资料和本次野外地质考察，该岩体由不同岩相组成（图 2），自岩体中部向外呈同心圆状展布: 中心相为斑状花岗闪长岩，中粗粒斑状结构，向外过渡为细中粒花岗闪长岩; 边缘相为细粒石英闪长岩（图 3）。不同岩相的黑云母和角闪石含量不同[9]，边缘相的黑云母和角闪石含量分别为15%和10%，过渡相分别为10%和5%~10%，中心相角闪石少见，黑云母含量为5%，由边部向内部暗色矿物逐渐减少，暗示岩浆9 演化程度越来越高。除此以外，还发育大量的南北向花岗闪长斑岩脉。
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图 2 太行山北段赤瓦屋地区地质简图Figure 2. Sketch geological map of Chiwawu area in Northern Taihang Mountain![]()
图 3 太行山北段赤瓦屋地区4 种不同岩性的手标本照片Figure 3. Photo for four different petrologic characters of granitoids in Chiwawu area of Northern Taihang Mountain此次野外观察可见，大小为2~10 m的黑色闪长质包体呈椭圆体和透镜状普遍发育于花岗闪长岩中，与寄主岩体边缘清楚。前人对太行山北段岩体开展过成矿潜力评价，赤瓦屋岩体的岩浆分异指数（DI）为75.04，轻重稀土元素比值(LREE/HREE)均较高，为20.2，黑云母MgO为12.80%~14.28%，石英Ti 含量为17×10-6，全岩的氧同位素为8.89%，暗示赤瓦屋岩体具有较大的成矿潜力[9]。早期资料显示该岩体有铜矿化，最近地勘队发现中心相斑状花岗闪长岩中发育铜钨多金属矿化，可见早阶段NE 向石英黄铁矿白钨矿脉和晚阶段SN 向黄铜矿脉，辉钼矿呈细脉浸染状产于岩体中，多与黄铜矿、黄铁矿共生。
3. 样品采集与测试方法
本次测年工作采集4 个不同岩性的样品，分别为石英闪长岩(CWW14)、花岗闪长岩(CWW2)、斑状花岗闪长岩(CWW12) 和花岗闪长斑岩脉(CWW1)，具体采样位置见图 2。将测年样品破碎后，经常规重力和磁选方法分选出锆石，在双目镜下挑纯。将待测锆石颗粒置于环氧树脂中制靶，然后磨至一半用于后期测试。锆石阴极发光在中国地质科学院地质研究所离子探针室HITACHIS3000-N型扫描电子显微镜上完成。在透射光、反射光显微镜观察及阴极发光研究的基础上，选择合适的锆石颗粒进行锆石U-Pb定年测试。
LA-MC-ICPMS 锆石U-Pb 定年测试分析在中国地质科学院矿产资源研究所MC-ICP-MS实验室完成，定年分析所用仪器为Finnigan Neptune型MC-ICPMS及与之配套的Newwave UP 213 激光剥蚀系统。所用激光剥蚀斑束直径为25 μm，频率为10 Hz，能量密度约为2.5 J/cm2，以He 为载气。信号较小的207Pb、206P、204Pb(+204Hg)、202Hg 用离子计数器(multi-ion-counters)接收，208Pb、232Th、238U信号用法拉第杯接收，实现了所有目标同位素信号的同时接收，并且不同质量数的峰基本上都是平坦的，可以获得高精度的数据。均匀锆石颗粒207Pb/206Pb、206Pb/238U、207Pb/235U的测试精度(2σ )均为2%左右，对锆石标准样品的定年精度和准确度在1%(2σ )左右。LA-MC-ICPMS 激光剥蚀采样采用单点剥蚀的方式，数据分析前用锆石GJ-1 调试仪器，使之达到最优状态，锆石U-Pb 定年以锆石GJ-1 为外标，U、Th含量以锆石M257(U: 923×10-6; Th: 439×10-6; Th/U:0.475)[16]为外标进行校正。测试过程中每测定5~7个样品前后重复测定2 个锆石标准样品，对样品进行校正，并测量一个锆石标准Plesovice，观察仪器的状态以保证测试精确度。数据处理采用ICPMSDataCal 程序，测量过程中绝大多数分析点206Pb/204Pb>1000，未进行普通铅校正，204Pb 由离子计数器检测，204Pb 含量异常高的分析点可能受包体等普通Pb 的影响，在计算时予以剔除，锆石年龄谐和图用Isoplot 3.0 程序获得。样品分析过程中，Plesovice 标样作为未知样品的分析结果为（337.3±1.1）Ma（n=5，2σ），对应的年龄推荐值为（337.13±0.37）Ma（2σ）[17]，两者在误差范围内完全一致，测试数据精度较好。
4. 分析结果
赤瓦屋不同岩相花岗质岩石的锆石U-Pb 分析测试结果见表 1，锆石U-Pb 谐和图见图 4。由图 4可知，石英闪长岩样品CWW14 锆石多呈长柱状，长为80~250 μm，宽为40~120 μm。本文对石英闪长岩中15 颗锆石进行年代学测试，Th 和U含量分别为100×10-6~306×10-6和150×10-6~347×10-6，其Th/U为0.4~1.5（表 1），谐和年龄为（134±1）Ma，MSWD=3.4; 加权平均年龄为（134±2）Ma，MSWD=0.62（图 4-a）。
表 1 太行山北段赤瓦屋铜钨矿区不同岩相的花岗质岩石的锆石U-Pb年龄测年结果Table 1. LA-ICPMS zircon U-Pb data of different petrofacies of granitoids in Chiwawu area,Northern Taihang Mountain
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图 4 太行山北段赤瓦屋地区不同岩相花岗质岩体锆石U-Pb谐和图Figure 4. Zircon LA-ICPMS U-Pb concordia diagrams for different petrofacies of granitoids in the Chiwawu area of NorthernTaihang Mountain花岗闪长岩样品CWW2 锆石多呈长柱状，锆石长20~320 μm，宽40~120 μm。本文分析了花岗闪长岩中23 颗锆石，Th 和U 含量分别为59.2×10-6~197×10-6 和105×10-6~289×10-6，其Th/U 为0.4~1.0（表 1），谐和年龄为（133±1）Ma，MSWD=2.3; 加权平均年龄为（133±2）Ma，MSWD=0.37（图 4-b）。
斑状花岗闪长岩样品CWW12锆石多呈长柱状，锆石长120~500 μm，宽80~100 μm。本文分析了斑状花岗长岩中12 粒锆石，Th 和U含量分别为88.6×10-6~492×10-6和227×10-6~596×10-6，其Th/U为0.3~0.8（表 1），谐和年龄为（131±2）Ma，MSWD=2.6; 加权平均年龄为（132±4）Ma，MSWD=0.68（图 4-c）。
花岗闪长斑岩脉样品CWW1锆石多呈长柱状，锆石长200~360 μm，宽10~100 μm。本文分析了斑状花岗长岩中28 粒锆石，Th和U含量分别为45.6×10-6~1303×10-6和83.1×10-6~775×10-6，其Th/U比值为0.4~1.7（表 1），谐和年龄为（128 ±1）Ma，MSWD=6.2; 加权平均年龄为（128±1）Ma，MSWD=2.4（图 4-d）。
5. 讨论
5.1 赤瓦屋岩体时代
赤瓦屋岩体位于太行山北段中生代岩浆带的南部（图 1-b），其形成时代受到高度关注。喻学惠等[5]提出该岩体由同心环状的不同岩相带（石英闪长岩、花岗闪长岩和斑状花岗闪长岩）组成，全岩Rb-Sr 等时线年龄为135.2 Ma；刘阳等[10] 利用SHRIMP测年获得该岩体北部和西部边缘相石英闪长岩的锆石U-Pb 年龄分别为（134.0±5.3）Ma 和（139.8±3.1）Ma；李林林等[12]获得该岩体西部边缘相石英闪长岩的LA-ICPMS 锆石U-Pb 年龄为(126.4±2.4) Ma。该岩体北部边缘相花岗闪长岩和闪长岩包体的LA-ICPMS 锆石U-Pb 年龄分别为(130±1.0) Ma和(128.2±1.5) Ma[13]。
如前文所述，赤瓦屋岩体除边缘相石英闪长岩外，还存在过渡相花岗闪长岩、中心相斑状花岗闪长岩和后期酸性岩脉，已有的锆石U-Pb 测年工作主要集中于边缘相[10, 12-13]。本文获得赤瓦屋岩体边缘相石英闪长岩、边缘相花岗闪长岩、中心相斑状花岗闪长岩和后期花岗闪长岩岩脉的锆石LAICPMS谐和年龄分别为（134 ±1）Ma、（133±1）Ma、（131±2）Ma和（128±1）Ma，其中本次边缘相的锆石U-Pb 年龄与前人获得的锆石U-Pb 年龄在误差范围内基本一致，表明本次测年数据是可靠的。本文测年数据表明，赤瓦屋岩体不同岩相体形成时代(134~131 Ma)在识差范围内基本一致，暗示岩浆经历了快速侵位、快速冷却结晶的地质过程，类似于邻区的麻棚岩体[12]。据野外实地观察，赤瓦屋岩体形成时代(134~131 Ma)略早于花岗闪长斑岩脉(128Ma)，这些与地质穿插关系观察一致。因此，赤瓦屋杂岩体形成于早白垩世，与太行山北段岩基和岩体的时代基本一致（见下文讨论）。
5.2 两期岩浆-成矿事件
由图 1-a 可知，NE向太行山北段岩浆带位于重力梯度带附近，其侵入岩的年龄一直受到高度关注，该带已有的晚中生代岩浆岩锆石U-Pb 年龄数据见表 2。由表 2 可知，太行山北段大河南岩基的石英二长岩的锆石U-Pb 年龄为127 Ma[18]；王安镇岩基中酸性岩浆和包体形成于132~126 Ma，东南部辉石闪长岩的锆石U-Pb 年龄为138 Ma[3, 18-19]；赤瓦屋岩体中酸性岩和包体形成于132~126 Ma[10, 12-13]；麻棚中酸性岩体和包体形成于131~124 Ma[6, 10, 12, 20]。除此之外，木吉村斑岩铜矿含矿岩体-闪长玢岩的锆石U-Pb 年龄为144.7 Ma[7]和144.1 Ma[21]，石湖金矿区石英闪长岩脉的锆石U-Pb 年龄为130 Ma[6]。由此可见，太行山北段晚中生代侵入岩存在2 期岩浆事件，分别为144~138 Ma和132~124 Ma，其中以第二期岩浆事件形成大面积的中酸性岩基和岩体为显著特征，而第一期岩浆事件形成的侵入岩规模相对较小，主要有集中分布于王安镇岩基东南部的辉石闪长岩和木吉村与斑岩铜矿成矿密切相关的闪长玢岩。最近研究表明：木吉村斑岩铜矿区的闪长玢岩是髫髻山火山旋回晚阶段次火山岩相的产物[7]，最新测年资料显示,太行山北段和燕山东部北东向发育的髫髻山组火山岩形成于晚侏罗世—早白垩世(151~131 Ma)[22]，这些火山岩可能是太行山北段第一期岩浆事件的产物。
表 2 太行山北段晚中生代侵入岩的锆石U-Pb年龄Table 2. Compilation of isotopic ages for important Late Mesozoic intrusions in Northern Taihang Mountain
太行山北段与晚中生代岩浆事件密切相关的成矿作用存在2 期矿化事件，第一期主要为与髫髻山组火山作用相关的斑岩铜钼多金属矿床，如木吉村大型斑岩铜钼矿（图 1-b），其辉钼矿Re-Os 模式年龄为(138.5±1.9) ~(142.7±2.0) Ma[21]，5 个辉钼矿Re-Os 样品等时线年龄为(142.5±1.4) Ma[7]；在其南侧10 km处的中型大湾斑岩型锌钼矿（图 1-b）的辉钼矿Re-Os模式年龄为(144.4 ± 7.4) Ma[23]。位于大河南与王安镇岩基之间大型安妥岭斑岩钼矿（图 1-b）的5 个辉钼矿Re-Os 样品等时线年龄为(147.3±3.7) Ma[8]或(147.8 ± 0.95) Ma[24]。
在第二期王安镇岩基周围发现了多个铜金矿床，如在木吉村矿区北侧的浮图峪矿田发现60 余处铜矿床（或矿点）（图 1-b），金矿床和矿点更是星罗棋布，遍及全区[5]，这些铜矿多为矽卡岩铜铁矿[4]。目前还缺少对这些中小型矽卡岩铜矿成矿时代的精确测年数据，根据含矿岩体的年龄推测，它们可能为第二期的产物。本次野外实地观察发现，赤瓦屋地区早阶段钨矿和晚阶段铜矿呈脉状产于岩体内部相的斑状花岗闪长岩中（（131 ±2）Ma），暗示钨铜矿化形成时代不早于131 Ma，赤瓦屋铜钨矿化是第二期成矿事件的产物。另外，在麻棚岩体南缘探明了与岩体密切相关的石英脉状金矿(石湖大型金矿)、隐爆角砾岩型银矿和斑岩钼矿[20]，石湖金矿区石英闪长岩脉的锆石U-Pb 年龄为130 Ma，石湖金矿热液钾长石K-Ar 年龄为132~120 Ma[6]，麻棚岩体周缘金银钼矿是第二期成矿事件的产物。由此可见，太行山北段晚中生代至少存在两期岩浆-成矿事件，具有较大的找矿潜力。与第一期斑岩型铜钼矿床相比，第二期成矿事件具有成矿类型多样性，晚中生代两期成矿事件特征类似于华南地区[25]。
6. 结论
（1）赤瓦屋岩体边缘相石英闪长岩、过渡相花岗闪长岩、中心相斑状花岗闪长岩和后期花岗闪长岩岩脉形成时代分别为(134 ± 1) Ma、(133 ±1) Ma、(131 ±2) Ma和(128 ±1) Ma，这些数据表明该岩体形成于早白垩世。
（2）太行山北段晚中生代存在两期岩浆-成矿事件，具有较大的找矿潜力。
致谢: 感谢项目组成员在野外的协助，西北大学大陆重点实验室以及中国地质调查局西安地质调查中心国土资源部岩浆作用成矿与找矿重点实验室工作人员在实验及测试上的指导与支持，在此一并感谢。 -
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图 1 热水钼多金属矿地质简图（图a据[36, 37]修改）
1—石炭系酸性熔岩组：浅肉红色流纹岩及灰绿色薄层粉砂岩，细砂岩夹灰岩；2—灰白—肉红色二长花岗岩；3—灰白—肉红色似斑状黑云母二长花岗岩；4—灰白色花岗闪长岩；5—灰绿色闪长岩、角闪闪长岩；6—断层；7—地质界线；8—铜矿化点；9—采样位置
Figure 1. Geological sketch map of the Reshui Mo polymetallic ore district
1-Carboniferous acidic lava group: light red rhyolite and celadon thin layer siltstone, fine sandstone with limestone; 2-Grayish white-red monzonitic granite; 3-Grayish white and red porphyritic monzonitic granite; 4-Grayish white granodiorite; 5-Diorite, hornblende diorite; 6-Fault; 7-Geological boundary; 8-Copper mineralized site; 9-Sampling location
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图 2 热水似斑状黑云母二长花岗岩野外及镜下显微结构照片
Kfs—钾长石；Mc—微斜长石；Pl—斜长石；Bt—黑云母；Q—石英
Figure 2. Outcrop picture and microstructure photographs of porphyroid biotite monzogranite from the Reshui ore district
Kfs-K-feldspar; Mc-Microcline; Pl-Plagioclase; Bt-Biotite; Q-Quartz
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图 4 似斑状黑云母二长花岗岩稀土元素配分模式图（球粒陨石标准化值据[42]）
Figure 4. Chondrite-normalized REE patterns of porphyroid biotite monzogranite
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图 5 似斑状黑云母二长花岗岩微量元素蛛网图（原始地幔标准化值据[43]）
Figure 5. Primitive mantle-mormoalized trace elemet spirder diagrams of porphyroid biotite monzogranite
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图 6 似斑状黑云母二长花岗岩锆石CL图像
Figure 6. Cl images of zircons from porphyroid biotite monzogranite
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图 7 似斑状黑云母二长花岗岩锆石U-Pb谐和图和加权平均年龄
Figure 7. Zircon U-Pb concordia diagram and histograms of weighted average ages of porphyroid biotite monzogranite
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图 9 似斑状黑云母二长花岗岩SiO2-Mg#图
1—压力7 kbar，温度：825~950℃环境下纯地壳的局部熔融(据文献[59])；2—压力7~13 kbar，温度：825~950℃环境下纯地壳的局部熔融(据文献[60])；3—压力8~16 kbar，温度1000~1050℃环境下纯地壳的局部熔融（据文献[56])
Figure 9. Porphyroid biotite monzogranite of SiO2-Mg# diagram
1-Pure crustal partial melt at 7kbar and 825~950℃(after reference [59]); 1-Pure crustal partial melt at 7~13 kbar and 825~950℃(after reference [60]; 3-Pure crustal partial melt at 8~16kbar and 1000~1050℃(after reference [56])
表 2 热水似斑状黑云母二长花岗岩微量元素（10-6）和稀土元素（10-6）
Table 2 Trace elements (10-6) and REE (10-6) of porphyroid biotite monzogranite
下载: 导出CSV
表 3 似斑状黑云母二长花岗岩LA-ICP-MS锆石U-Th-Pb同位素测试结果
Table 3 LA-ICP-MS zircon U-Th-Pb isotope analytical results of porphyroid biotite monzogranite
下载: 导出CSV
表 4 热水地区印支期含矿岩体（矿床）年龄及测试方法
Table 4 Age of Indosinian ore-beariang rock mass and testing method
下载: 导出CSV
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