Chronology and geochemistry of Mogutu granite in Inner Mongolia and its effect of crustal extension and thinning
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摘要:
莫古吐花岗岩体位于大兴安岭南段黄岗梁-甘珠尔庙锡多金属成矿带西南端，其岩性主要以黑云母钾长花岗岩为主。文章通过LA-ICP-MS锆石U-Pb定年及岩石地球化学研究分析，探讨莫古吐花岗岩的成因类型、岩浆源区及成岩构造背景。锆石U-Pb年代学研究表明，莫古吐岩体形成于148.8~152.7 Ma，属晚侏罗世岩浆产物。岩石学及地球化学特征显示，莫古吐花岗岩属于碱性-弱过铝质系列，具有富SiO2（73.64%~80.86%），富K2O（2.6%~6.0%），贫Al2O3（10.57%~13.88%）的特点，富集Rb、U、Th等大离子亲石元素，亏损P、Ti、Ba、Sr等元素，稀土配分型式呈燕式分布，δEu值为0.10~0.27，负Eu异常明显，锆石饱和温度较高，为795~911℃，属于高演化A型花岗岩。结合年代学、地球化学数据及前人研究成果，认为莫古吐花岗岩体的岩浆源区较浅，成岩物质主要以壳源物质为主，岩体形成于地壳伸展-减薄的构造环境中，与蒙古-鄂霍茨克洋构造体制的关系更为密切。
Abstract:The Mogutu granite pluton is emplaced in the southwest Huanggangliang to Ganzhuermiao tin-polymetal metallogenic belt in Southern Da Hinggan Mountains, which is mainly composed of biotite moyite. The genetic type, magmatic source region and diagenetic tectonic setting of the Mogutugranite were studied by U-Pb dating of zircon in LA-ICP-MS and petrogeochemical analysis. Zircon LA-ICP-MS dating of the biotite moyite yields a concordant age of 148.8-152.7Ma, which means that the Mogutu granite pluton was formed in Late Jurassic. The Mogutu granites is characterized by weak peraluminous and alkaline, high content of SiO2 (73.64%-80.86%), K2O(2.6%-6.0%), but low content of Al2O3 (10.57%-13.88%), depletion in P、Ti、Ba、Sr, and enrichment Rb、U、Th. The chondrite-normalized patterns of REE are in seagull forms, with strong negative Eu anomalies, with 0.10 to 0.27 of δEu, and higher zircon saturation temperatures(795-911℃), which indicates that the Mogutu pluton is similar to A-type granite. Therefore, the Moguto granites shows highly fractionated A -type granite affinity. Based on the previous research results, it is inferred that the depth of magma source of Mogutu granite pluton is shallow, the magmatic substance was derived from the crust, and the granite pluton was emplaced in the tectonic setting of crustal extension and thinning more likely related to the closure of the Mongol-Okhotsk tectonic belt.
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1. 研究目的(Objective)
锗(Ge)是一种典型的稀散元素，其地壳丰度为1.5×10-6，主要富集在煤和铅锌矿床中。统计结果显示，闪锌矿是铅锌矿床中Ge的主要载体矿物，但不同类型铅锌矿床闪锌矿中Ge的含量存在差异。除热液脉型和浅成热液型铅锌矿床闪锌矿中Ge的含量较高(可达2500×10-6)外，其他主要类型(如喷流沉积型，SEDEX；火山块状硫化物型，VMS；密西西比河谷型，MVT，等)铅锌矿床闪锌矿中Ge的平均含量通常 < 300×10-6。本次发现贵州贵定竹林沟锌矿床闪锌矿中Ge的显著超常富集现象，现报道如下。
2. 研究方法(Methods)
在细致深入的矿床学和矿物学研究基础上，利用激光剥蚀等离子质谱仪(LA-ICP-MS)对竹林沟锌矿床主要金属矿物闪锌矿进行原位微量元素组成分析。统计闪锌矿中Ge等元素的富集特征，结合相关分析和以往研究成果，揭示竹林沟锌矿床中Ge的超常富集机制。
3. 研究结果(Results)
竹林沟锌矿床闪锌矿中Ge的含量为592×10-6~1100×10-6(平均764×10-6，表 1)，锌矿石中Ge的平均品位97.9×10-6。闪锌矿LA-ICP-MS微区原位Ge含量分析资料显示，扬子板块及其周缘地区MVT铅锌矿床，如牛角塘、会泽、毛坪、富乐等，其闪锌矿中Ge的含量均 < 652×10-6，即便富乐矿床闪锌矿中Ge的含量最高，但其平均含量也仅为191×10-6，明显比竹林沟锌矿床闪锌矿中Ge的含量(特别是Ge的平均含量)低。
表 1 竹林沟锌矿床闪锌矿部分元素含量(10-6)Table 1. The part elemental contents of sphalerite from the Zhulingou Zn deposit(10-6)
与世界上主要类型铅锌矿床闪锌矿LA-ICP-MS微区原位Ge含量分析资料相比，竹林沟矿床闪锌矿中Ge的含量比SEDEX(Ge含量通常 < 50×10-6)、VMS(Ge含量多数 < 100×10-6)和MVT(Ge含量n×10-6~n×102×10-6，Ge平均含量 < 300×10-6)等闪锌矿中Ge的含量高出一个数量级。竹林沟矿床闪锌矿中Ge的含量与法国Noailhac-Saint Salvy热液脉型Zn-Ge-Ag-Pb-Cd矿床(Ge平均含量750×10-6)和玻利维亚Porco浅成热液型Ag-Zn-Pb-Sn-Ge矿床(n×102×10-6~2500×10-6)等少数类型铅锌矿床闪锌矿中Ge的含量(特别是Ge的平均含量)相当。
可见，竹林沟锌矿床闪锌矿中Ge的含量比目前已知扬子板块及其周缘地区MVT矿床闪锌矿中Ge的含量(特别是Ge的平均含量)都高，且明显高出全球主要类型(除岩浆热液型和热液脉型外)铅锌矿床闪锌矿中Ge的含量(特别是Ge的平均含量)一个数量级，具有显著超常富集特征(接近Ge地壳丰度的1000倍)。
初步分析显示，竹林沟锌矿床闪锌矿中Zn与Ga和Cd之间具有正相关关系；相反，Fe与Ga和Cd之间均具有负相关关系，这表明该矿床闪锌矿中Ga和Cd很可能不是直接替代Zn而是替代Fe，与笔者前期认识基本一致。然而，不难发现该矿床闪锌矿中Zn与Ge之间呈一定的负相关关系，但Fe和Ge之间则呈一定的正相关关系，进一步地Zn与Fe之间具有显著的负相关关系，且Zn与Fe+Ge之间负相关性更显著(图 1)。目前，闪锌矿中主要有六种Ge替代Zn的方式：(1)2Cu++Cu2++Ge4+↔4Zn2+；(2)Ge2+↔Zn2+；(3)2Ag++Ge4+↔3Zn2+；(4)2Cu++Ge4+↔3Zn2+；(5)□(晶体空位)+Ge4+↔2Zn2+；(6)nCu+Ge↔(n+1)Zn。可见，这六种替代方式均不能解释竹林沟锌矿床闪锌矿Zn和Fe+Ge之间的强烈负相关关系。因此，笔者推测该矿床中Ge很可能是与Fe一起共同替代Zn进入闪锌矿晶格(Fe+Ge↔2Zn)，是一种新的Ge替代方式。
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图 1 竹林沟锌矿床闪锌矿Zn-(Fe+Ge)相关图解Figure 1. Relationship diagram of sphalerite Zn-(Fe+Ge)in the Zhulingou Zn deposit4. 结论(Conclusions)
竹林沟锌矿床闪锌矿中显著超常富集锗，锗的富集程度接近1000倍，且锗与铁一起共同替代锌进入闪锌矿晶格，是一种新的锗替代方式。初步估算竹林沟锌矿床锗金属储量超过400 t，而竹林沟锌矿床外围还有半边街等锌矿床，初步预测研究区锗资源量可能达到超大型规模(>1000 t)，一个新的国家级乃至世界级锗资源基地曙光已现。
5. 致谢(Acknowledgments)
感谢科技部、国家自然科学基金委、云南省科技厅和云南大学对本项目的支持。
致谢: 野外地质工作得到北京矿产地质研究院蒋斌斌、管育春等工程师的大力支持和帮助；测试工作得到合肥工业大学矿床成因与勘查技术研究中心矿物微区分析实验室汪方跃老师的热情帮助；审稿专家给论文提出了许多建设性的意见，特此感谢！ -
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图 1 中国东北区域构造单元划分（a，据Wu et al., 2011）、莫古吐地区区域地质图（b，据项目组内部资料修编）
1—满克头鄂博组晶屑凝灰岩、凝灰质角砾岩；2—新民组粉砂岩、细砂岩、砂砾岩；3—林西组粉砂岩、板岩；4—哲斯组变质粉砂岩、钙质砂岩、大理岩、硅质岩、粉砂质板岩；5—大石寨组安山岩、细碧岩；6—辉长岩；7—流纹斑岩；8—闪长岩；9—花岗斑岩；10—黑云母二长花岗岩；11—黑云母花岗岩；12—黑云母钾长花岗岩；13—整合接触；14—断裂及编号（F1—蒙古—鄂霍茨克断裂；F2—德尔布干断裂；F3—贺根山断裂；F4—西拉木伦断裂；F5—康保—赤峰断裂；F6—嫩江八里罕断裂；F7—佳木斯—伊通断裂）；15—金属矿床；16—采样位置；17—研究区
Figure 1. Tectonic subdivisions of northeastern China(a, after Wu et al., 2011); Regional geological map of the Mogutu area (b, after internal materials)
1- Crystal tuff and tuffaceous breccia of the Manketouerbo Formation; 2- Siltstone, fine sandstone and glutenite of the Xinmin Formation; 3- Siltstone and slate of the Linxi Formation; 4- Metamorphic siltstone, calcareous sandstone, marble, siliceous and silty slate of the Zhesi Formation; 5- Andesite and spilite of the Dashizhai Formation; 6- Gabbro; 7- Rhyolite porphyry; 8- Diorite; 9- Granite porphyry; 10- Biotite adamellite; 11- Biotite- granite; 12- Biotite moyite; 13- Conformity; 14- Fracture and No. (F1- Mongolia Okhotsk fracture; F2- Deerbugan fracture; F3- Hegenshan fracture; F4 − Xilamulun fracture; F5- Kangbao- Chifeng fracture; F6- Nengjiang- Balihan fracture; F7-Jiamusi—Yitong fracture); 15-Ore deposit; 16-Sampling position; 17-Researched area
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图 2 莫古吐花岗岩野外照片
a—浅肉红色黑云母钾长花岗岩；b—灰白色黑云母钾长花岗岩；c—烟灰色石英；d—团块状黑云母；e—伟晶结构；f—晶洞构造；g—萤石；h—电气石
Figure 2. Photographs of Mogutu granite
a-Yellowish pink biotite moyite; b-Gray biotite moyite; c-Smoky quartz; d-Biotite briquettes; e-Pegmatitic texture; f-Miarolitic strecture; g-Fluorite; h-Tourmaline
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图 3 莫古吐花岗岩显微镜下照片
a—浅肉红色黑云母钾长花岗岩正交偏光镜下照片(+)；b—灰白色黑云母钾长花岗岩正交偏光镜下照片(+)；c—正长石的卡氏双晶(+)；d—微斜长石交代溶蚀斜长石及斜长石发育卡钠复合双晶(+)；e—绢云母呈斜长石假象发育(+)；f—黑云母绿泥石化，并析出磁铁矿（−）；Qz—石英；Bi—黑云母；Pl—斜长石；Kf—钾长石；Pth—条纹长石；Mt—磁铁矿；Ser—绢云母化；（+）—正交偏光；（−）—单偏光
Figure 3. Microphotographs of Mogutu granite
a- Yellowish pink biotite moyite; b- Gray biotite moyite; c- Carlsbad twin law of orthoclase; d- Plagioclase was absorbed by the microcline and carlsbadal bite compound twin of plagioclase; e- Sericite appears to develop in the illusion of plagioclase; f- Magnetite precipitation of biotite mainly results from epidotization; Qz-Quartz; Bi-Bitite; Pl-Plagioclase; Kf-K-feldspar; Pth-Perthite; Mt-Magnetite; Ser-Sericitization; (−)-Plane polarization; (+)-Orthogonal polarization
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图 4 莫古吐花岗岩体锆石阴极发光图（CL）图像及测试位置
Figure 4. Cathodoluminescence images of representative zircons and measuring positions of the Mogutu granite pluton
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图 5 莫古吐花岗岩体锆石U−Pb谐和图
Figure 5. Zircon U-Pb age and its concordia diagram of the Mogutu granite body
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图 6 莫古吐花岗岩TAS分类图解（据Middlemost, 1994）
Figure 6. TAS diagram of the Mogutu granite(after Middlemost, 1994)
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图 7 莫古吐花岗岩SiO2−AR岩石系列判别图（据Rickwood, 1989）和A/CNK−ANK图解（据Maniar and Piccoli, 1989）
Figure 7. SiO2−AR discriminant diagram (after Rickwood, 1989) and A/CNK−ANK Diagram (after Maniar and Piccoli, 1989) of the granite
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图 8 莫古吐花岗岩稀土元素球粒陨石分布型式图（a）及微量元素原始地幔标准化蜘蛛图（b）
(标准化数据据文献Sun and Mcdonough, 1989)
Figure 8. Chondrite-normalized REE pattern(a) and primitive mantle-normalized spider diagram(b)of the Mogutu granite
(chondrite and primitive mantle normalized values after reference Sun and Mcdonough, 1989)
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图 9 莫古吐花岗岩Rb−Sr−Ba图解（据Müller and Groves, 2001）
Figure 9. Rb−Sr−Ba triangular diagram of the Mogutu granite (after Müller and Groves, 2001)
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图 10 104×Ga/Al−(Na2O+K2O)图解（a）与104×Ga/Al−Zr图解（b）(底图据Joseph et al., 1987)
Figure 10. 104×Ga/Al−(Na2O+K2O) diagram(a) and 104×Ga/Al−Zr diagram of the Mogutu granite(b)(after Joseph et al., 1987)
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图 11 莫古吐花岗岩δEu−La/Yb图解(底图据文献Joseph et al., 1987)
Figure 11. δEu−La/Yb diagram of the Mogutu granite (after reference Joseph et al., 1987)
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图 12 莫古吐花岗岩Nb−Ce−Y构造环境判别图解（底图据文献Pearce et al., 1984）
A1—非造山花岗岩；A2—造山后花岗岩
Figure 12. Nb−Ce−Y discrimination diagram of tectonic setting of the Mogutu granite(after reference Pearce et al., 1984)
A1-anorogenic granite; A2-post-orogenic granite
表 2 莫古吐花岗岩体主量元素（%）和微量元素（10−6）组成
Table 2 Major element (%) and trace element (10−6) composition of the Mogutu granite
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