Occurrence of cobalt and its geological significance in the Qibaoshan Co-Pb-Zn deposit, central segment of the Jiangnan orogenic belt
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摘要:
钴（Co）是一种重要的战略性矿产，其赋存状态是当前国际矿床学研究的热点之一。七宝山钴铅锌矿床位于江南造山带中段，矿体受高岽山背斜核部次级褶皱控制、呈NE向透镜状或似层状展布。但目前该矿床钴的赋存状态研究薄弱。对不同中段矿石开展扫描电镜−能谱（SEM-EDS）和电子探针（EPMA）矿物成分分析，结果表明Co主要赋存在斜方砷钴矿、辉砷钴矿、方钴矿和硫镍（铜）钴矿等独立钴矿物中，少量以类质同象形式进入细粒黄铁矿和斜方砷镍矿晶格。斜方砷镍矿幔部常被斜方砷钴矿交代，边部被辉砷钴矿和辉砷镍矿交代；辉砷钴矿和硫镍（铜）钴矿也常沿黄铜矿边部交代。研究确定早期成矿流体砷活性较高，形成斜方砷镍矿、斜方砷钴矿和方钴矿；随着成矿流体砷活性降低，硫活性增加，晚期形成辉砷钴矿和硫镍（铜）钴矿。该矿床的钴镍矿物交代结构及组合与典型“五元素脉”型矿床具有一定的相似性。因此，七宝山矿床应为具有“五元素脉”特征的热液脉型钴矿床。
Abstract:Objective Cobalt is an important strategic metal, crucial for new energy technologies. Understanding its occurrence in ore deposits represents a key focus of international ore deposit research. The Qibaoshan Co-Pb-Zn deposit, located in the central segment of the Jiangnan orogenic belt, features ore bodies controlled by secondary folds within the core of the Gaodongshan anticline, which exhibit NE-trending lenticular or stratoid shapes. However, the occurrence state of cobalt in this deposit remains poorly constrained.
Methods In this study, ore samples collected from different levels of the open pit were analyzed using backscattered electronc (BSE) imaging, energy dispersive X-ray spectroscopy (EDS), and electron probe microanalysis (EPMA).
Results The results show that cobalt occurs predominantly as independent minerals, including safflorite, cobaltite, skutterudite, and siegenite. Minor cobalt is hosted in solid solution within fine-grained pyrite and rammelsbergite. Rammelsbergite commonly exhibits mantles replaced by safflorite, and both minerals are in turn replaced at their rims by cobaltite and gersdorffite. Cobaltite and Cu-bearing siegenite also frequently replace the margins of chalcopyrite. These mineralogical relationships indicate that the early-stage ore-forming fluids were characterized by high arsenic activity, leading to the precipitation of rammelsbergite, safflorite, and skutterudite. As mineralization proceeded, arsenic activity decreased while sulfur activity increased, resulting in the formation of cobaltite and siegenite during the late stage.
Conclusions The replacement textures and mineral assemblages of Co-Ni minerals in the Qibaoshan deposit resemble those typical of "five-element vein"-type deposits. Therefore, the Qibaoshan deposit is classified as a hydrothermal vein-type Co-Pb-Zn deposit with characteristics of "five-element vein".
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图 2 七宝山钴铅锌矿区地质图(a)及7号勘探线剖面图(b)
Figure 2. Geological map of the Qibaoshan Co-Pb-Zn deposit (a) and cross-section of Line 7 (b)
图 3 七宝山钴铅锌矿床矿石特征
a. 早期石英-粗粒黄铁矿阶段，石英与粗粒黄铁矿共生；b. Co-Ni砷化物阶段原生钴矿物后期被氧化成钴华；c. 铜矿石，黄铜矿常与辉砷钴矿共生；d. 方铅矿和闪锌矿与细粒黄铁矿共生；e. 晚期石英脉含星点状方铅矿；f. 碳酸盐阶段白云石与菱铁矿共生
Figure 3. Characteristics of ores in the Qibaoshan Co-Pb-Zn deposit
图 4 七宝山钴铅锌矿石镜下照片
a. 毒砂与粗粒黄铁矿（PyⅠ）共生, 闪锌矿交代早阶段的毒砂；b. PyⅠ被细粒黄铁矿（PyⅡ）交代；c. 斜方砷钴矿呈星状结构；d. 树枝状斜方砷镍矿；e. 辉砷钴矿交代斜方砷钴矿；f. 辉砷钴矿沿黄铜矿边部交代；g. 黄铜矿、辉砷钴矿和砷黝铜矿共生；h. 黄铜矿交代硫镍（铜）钴矿；i. 闪锌矿、方铅矿和黄铜矿共生，方铅矿交代黄铜矿；PyⅠ. 粗粒黄铁矿；Apy. 毒砂；PyⅡ. 细粒黄铁矿；Ram. 斜方砷镍矿；Saf. 斜方砷钴矿；Cbt. 辉砷钴矿；Sig. 硫镍（铜）钴矿；Ccp. 黄铜矿；Td. 砷黝铜矿；Sp. 闪锌矿；Gn. 方铅矿；下同
Figure 4. Microscopic photographs of ores in the Qibaoshan Co-Pb-Zn deposit
图 6 七宝山钴铅锌矿床硫砷化物BSE和能谱图
a.方铅矿交代PyⅠ；b. 斑铜矿沿黄铜矿边部交代、方铅矿再交代黄铜矿和斑铜矿；c. 斜方砷钴矿和辉砷钴矿交代PyⅠ；d. 斜方砷镍矿幔部被斜方砷钴矿和辉砷镍矿交代；e, f. 斜方砷钴矿镜下和BSE照片，显示辉砷钴矿交代斜方砷钴矿；g. 斜方砷钴矿能谱图；h. 硫镍（铜）钴矿交代黄铜矿；i. 斜方砷钴矿、方钴矿和辉砷钴矿环带交代结构；j. 辉砷钴矿能谱图；Skt. 方钴矿；Ger. 辉砷镍矿；Bn. 斑铜矿；cps. 每秒计数；Energy. 能量；下同
Figure 6. BSE images and energy spectra of sulfides and arsenides in the Qibaoshan Co-Pb-Zn deposit
图 7 七宝山钴铅锌矿床硫化物相对质量分数箱线图
Figure 7. Box plot of osulfide relative mass fraction in the Qibaoshan Co-Pb-Zn deposit
图 8 七宝山钴铅锌矿床（含）钴矿物质量分数箱式图
Figure 8. Box plot of cobalt mineral mass fraction in the Qibaoshan Co-Pb-Zn deposit
图 9 七宝山钴铅锌矿床辉砷钴矿CoAsS-FeAsS-NiAsS三元图解
Figure 9. CoAsS-FeAsS-NiAsS ternary diagram of cobaltite in the Qibaoshan Co-Pb-Zn deposit
图 10 七宝山钴铅锌矿床不同类型硫砷化物矿物钴与镍和铁、硫与砷含量关系图
Figure 10. Relationships between the content of cobalt and nickel and iron, sulfur and arsenic in different types of sulfides and arsenides minerals in the Qibaoshan Co-Pb-Zn deposit
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