Characteristics and Uenesis of Carrollite from Mylonite-type Oreshoot of the Hongtoushan Deposit
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摘要:
钴是一种非常重要的关键资源，但中国钴资源却非常稀少，对外依存度居高不下。火山岩成因块状硫化物（VMS）矿床是钴资源的重要来源之一，其中钴的赋存状态及钴矿物成因仍存在较大争议。红透山是中国最古老的VMS矿床，除含有丰富的铜锌和金资源外，还伴生有一定的钴资源。细致的矿相学工作发现，红透山矿床中的钴多以伴生形式存在于硫化物中，最典型的就是糜棱岩型富矿石存在的钴独立矿物——硫铜钴矿。岩相学和矿物地球化学结果显示，红透山矿床糜棱岩型富矿石中的硫铜钴矿可分为早阶段的他形粒状、中阶段自形粒状和晚阶段自形-半自形脉状。三类硫铜钴矿的产出特征相似，化学组成相近，应为同期热液作用不同阶段的产物。在变质变形和热液叠加过程中，分散于原生VMS矿石中的黄铁矿等硫化物中的钴发生再活化，随着热液活动聚集到糜棱岩型富矿石中并最终形成硫铜钴矿。本次工作为红透山糜棱岩型富矿石中钴的资源评价与综合利用提供了矿物学基础。
Abstract:Cobalt is a critical strategic mineral resource and remain significant concerns in China due to the scarcity and heavy reliance on foreign countries. Volcanic-hosted massive sulfide (VMS) deposits are significant sources of cobalt resources. However, the occurrence state of cobalt and the genesis of cobalt minerals are still under debate. The Hongtoushan deposit, the oldest VMS deposit in northeast China, contains numerous Cu, Zn, and Au resources, as well as some cobalt resources. Based on systematic mineralogy observation by microscope and TESCAN Integrated Mineral Analyze (TIMA), the sulfide paragenesis and carrollite was identified in mylonite-type oreshoot of the Hongtoushan deposit. Additionally, TIMA and geochemistry analysis by electronic microprobe analysis (EMPA) show that carrollite grains in the mylonite-type oreshoot of Hongtoushan could be divided into early-stage anhedral granular, mid-stage euhedral granular, and late-stage subhedral-euhedral veined. These three types of carrollite grains have similar mineral characters and geochemical contents and thus might be products of different stages during one hydrothermal event. Through deformation under regional metamorphism and overprinting during later hydrothermal event, cobalt scattered in sulfide minerals was remobilized from VMS orebodies to hydrothermal with enrichment of Cu, Co, and Au. The Co-enriched hydrothermal solution transports through schistose and faults in mylonite VMS orebodies and wall rocks, formed carrollite grains and mylonite-type oreshoot eventually. This study provides a mineralogical basis for resource evaluation and comprehensive utilization of cobalt in the Hongtoushan deposit.
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Key words:
- carrollite /
- occurrence /
- remobilization /
- metamorphic hydrothermal /
- the Hongtoushan deposit
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图 1 红透山矿床大地构造位置（a）及矿体–167 m中段纵投影图（b）（据Gu et al., 2007）
Figure 1.
表 1 样品信息表
Table 1. Sample information
编号 名称 位置 矿石类型 矿物组成 HT-312 富铜矿石 14线–647 m中段矿体边部 糜棱岩型富矿石 黄铜矿、闪锌矿 HT-310 富铜矿石 14线–647 m中部矿体中部 糜棱岩型块状富矿石 黄铜矿、闪锌矿、硫铜钴矿等 
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表 2 糜棱岩型富矿体中硫铜钴矿中电子探针分析结果（%）及化学式
Table 2. EPMA data and chemical formular of corrallite from mylonite-type high-grade ore
类型 编号 S Cu Co Ni Fe Total 化学式 早阶段 12-19-13 40.211 12.984 39.123 4.860 0.663 98.577 Cu0.652（Co, Ni）2.382S4 12-19-18 40.074 12.511 37.749 4.781 0.574 98.681 Cu0.63（Co, Ni）2.343 S4 12-19-26 41.48 13.285 38.859 5.309 1.054 100.464 Cu0.645（Co, Ni）2.319 S4 12-19-27 41.238 12.780 39.311 5.382 0.532 99.920 Cu0.626（Co, Ni）2.360 S4 12-19-28 41.733 13.101 39.067 5.116 0.645 100.204 Cu0.634（Co, Ni）2.305 S4 10-11-13 40.986 13.925 38.365 4.963 0.074 98.947 Cu0.686（Co, Ni）2.302S4 10-11-14 41.231 14.677 38.508 4.861 0.055 99.908 Cu0.719（Co, Ni）2.290 S4 10-11-15 41.128 14.655 38.837 4.795 0.180 100.196 Cu0.719（Co, Ni）2.310S4 中阶段 12-19-14 41.261 12.943 39.306 5.277 0.678 100.332 Cu0.633（Co, Ni）2.353 S4 12-19-15 41.41 13.224 39.770 4.878 0.692 100.499 Cu0.645（Co, Ni）2.348 S4 12-19-16 40.949 12.536 38.597 5.123 0.787 98.576 Cu0.618（Co, Ni）2.325 S4 12-19-17 40.994 12.925 38.759 5.288 0.903 99.522 Cu0.636（Co, Ni）2.340 S4 10-11-16 41.006 14.336 38.350 4.924 0.141 99.358 Cu0.706（Co, Ni）2.298S4 10-11-17 41.311 14.367 38.592 4.742 0.131 99.869 Cu0.702（Co, Ni）2.284S4 10-11-18 40.817 14.494 38.619 4.743 0.146 99.357 Cu0.717（Co, Ni）2.311S4 10-11-19 40.925 14.521 38.649 4.705 0.148 99.022 Cu0.716（Co, Ni）2.276S4 10-11-20 40.878 14.411 38.678 4.668 0.087 98.756 Cu0.712（Co, Ni）2.278S4 10-11-21 41.361 14.792 38.708 4.630 0.675 100.464 Cu0.722（Co, Ni）2.265S4 10-11-22 40.868 13.900 38.738 4.592 0.181 99.017 Cu0.687（Co, Ni）2.322S4 10-11-23 40.648 13.913 38.767 4.554 0.397 98.986 Cu0.691（Co, Ni）2.325S4 10-11-24 41.606 14.771 38.797 4.516 0.534 100.646 Cu0.717（Co, Ni）2.257S4 10-11-25 41.231 14.557 38.826 4.478 0.245 100.08 Cu0.713（Co, Ni）2.282S4 10-11-26 42.023 14.618 38.856 4.440 1.424 100.57 Cu0.702（Co, Ni）2.172S4 晚阶段 12-19-9 41.331 13.110 39.047 5.097 0.874 100.124 Cu0.64（Co, Ni）2.326 S4 12-19-10 41.084 13.074 39.165 5.155 0.684 99.864 Cu0.642（Co, Ni）2.349S4 12-19-11 41.244 12.917 38.486 5.329 0.648 99.198 Cu0.632（Co, Ni）2.313 S4 12-19-22 40.948 12.557 38.797 5.219 0.635 98.866 Cu0.619（Co, Ni）2.341 S4 12-19-24 41.237 12.990 38.370 4.761 0.698 98.797 Cu0.636（Co, Ni）2.277 S4 10-11-11 41.045 14.303 38.368 4.876 0.110 99.253 Cu0.703（Co, Ni）2.294 S4 10-11-12 41.197 14.744 37.317 4.696 0.067 98.666 Cu0.722（Co, Ni）2.221 S4 12-19-23 40.692 12.496 37.465 4.789 0.835 97.924 Cu0.62（Co, Ni）2.261 S4 平均值 41.102 13.691 38.672 4.889 0.499 99.505 Cu0.678（Co, Ni）2.289 S4
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