Heavy minerals, Sr-Nd isotopic composition of sandy land in Hulun Buir, Inner Mongolia and their implications for Asian aeolian dust system
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摘要:
呼伦贝尔沙地作为中国北方沙漠的重要组成部分，对其物质组成的深入探讨对于亚洲风尘系统的研究具有重要意义。重矿物特征和Sr-Nd同位素组成是解开沉积物演化过程和物源示踪的重要工具，但分选作用所造成的"粒度效应"一直是沙地重矿物和Sr-Nd同位素组成的制约因素。为分析呼伦贝尔沙地的物质组成及探讨分选作用对重矿物和Sr-Nd同位素组成的影响，采集了呼伦贝尔沙地19个风成沙和河流沙样品，并进行了分粒级处理。其中，对12个子样（< 73 μm和73~125 μm两个粒级）进行了重矿物的鉴定分析，对23个子样（< 63 μm、 < 30 μm和 < 11 μm三个粒级）进行了Sr-Nd同位素的测定。结果表明：不同粒度组分的重矿物含量、重矿物指数（ATi、GZi和ZTR）和重矿物组合存在明显差异；稳定和极其稳定矿物优先富集于细颗粒，使细颗粒沉积物的总体稳定程度加强。与以往Sr-Nd同位素粒度控制的研究结果不同，本文研究结果显示，87Sr/86Sr比值受粒度的影响很小，但Nd同位素组成明显受粒度效应的影响，并表现出粗颗粒组分有更高Nd同位素比值的趋势。Sr-Nd同位素组成存在时间效应，随时间发生变化，表明了风尘源区地球化学组成的不稳定性，这对于利用重矿物和Sr-Nd同位素进行亚洲风尘系统研究具有重要指示，在物源示踪时必须考虑宽/多粒度窗口以及充足的样品量以弥补粒度和时间效应带来的偏差。
Abstract:As an important part of Northern China Desert, Hulun Buir sandy land is of great significance to the study of dust system in Asia. The characteristics of heavy minerals and the composition of Sr-Nd isotopes are the important tools to reveal the sediment evolution process and trace the provenance. But the "grain size effect" caused by sedimentary sorting has always been the limiting factor for the composition of heavy minerals and Sr-Nd isotopes in sandy land. Totally 19 aeolian sand and fluvial sand samples were collected from Hulun Buir sandy land and screened to analyze the material composition and discuss the effect of separation on the composition of heavy minerals and Sr-Nd isotopes. Among them, 12 sub-samples (< 73 μm and 73-125 μm) were identified and analyzed for heavy minerals, and 23 sub-samples (< 63 μm, < 30 μm and < 11 μm) were determined for Sr-Nd isotopes. The results show that there are significant differences in heavy mineral content, heavy mineral index (ATi, GZi and ZTR) and heavy mineral assemblage with different particle sizes. The stable and extremely stable minerals are concentrate preferentially onto the finer particles, which enhances the overall stability of the fine-grained sediments. Different from previous studies on Sr-Nd isotopic grain size control, our results show that the 87Sr/86Sr ratio is slightly affected by the grain size effect, but the Nd isotopic composition is significantly affected by it, and the coarse-grained components tend to have a higher Nd isotopic ratio. The Sr-Nd isotopic composition of Hulun Buir sandy land has "time effect". It shows that the geochemical composition of the dust source area is unstable. This study is of great significance for the understanding of Asian aeolian dust system study using heavy mineral and Sr-Nd isotopic composition. The wide or multiple grain size window as well as substantial amount of samples must be considered for source tracing.
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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: 河北廊坊诚信地质公司的张佩萱、李鹏、王晓飞、周佳、张云丹、李必成和刘铮等做了大量的样品测试工作，吴鹏和魏振宇参加了呼伦贝尔沙地的部分野外取样，张月馨、张曼和刘璐参与了样品的分粒级处理，在此一并表示衷心的感谢! -
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图 1 呼伦贝尔沙地地貌及采样位置示意图
Figure 1. Topography of Hulun Buir sandy land, showing the sampling location of the study area
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图 2 呼伦贝尔沙地两粒级组分重矿物含量偏差（RD）图
Figure 2. Comparison of relative deviation (RD) contents of two kinds of particles heavy mineral
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图 3 呼伦贝尔沙地两个组分稳定性对比图
Figure 3. Comparison of stability of two components in Hulun Buir sandy land
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图 5 呼伦贝尔沙地不同粒度Sr-Nd同位素组成与中国北方边界沙漠、黄土高原黄土Sr-Nd同位素组成对比
Figure 5. Sr-Nd isotopic compositions of the Hulun Buir sandy land, in comparison with those of the loess in the CPL, the deserts around northern boundary of China
表 1 呼伦贝尔沙地重矿物种类及含量（%）
Table 1 Heavy mineral types and contents in Hulun Buir sandy land(%)
下载: 导出CSV
表 4 呼伦贝尔沙地的Sr-Nd同位素组成
Table 4 Sr and Nd isotopic compositions of the Hulun Buir sandy land
下载: 导出CSV
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