金川超大型铜镍矿床钴的赋存状态与富集过程研究
Study on the Occurrence State and Enrichment Process of Cobalt in Jinchuan Giant Magmatic Ni−Cu Sulfide Deposit
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摘要:
金川矿床位于龙首山隆起带东段，是中国最大的岩浆镍钴（铂族元素）矿床。该矿床中最重要的金属硫化物组合是磁黄铁矿、镍黄铁矿和黄铜矿，仅局部含有微量的辉钴矿等独立钴矿物。全岩成矿元素分析显示：矿石中Co与S、Ni之间呈良好的正相关性，与As相关性较差，Co/Ni随硫化物含量的增加而降低。电子探针分析结果表明：镍黄铁矿中Co含量较高，其含量为0.32%～1.93%，平均为0.81%；磁黄铁矿和黄铜矿（方黄铜矿）中Co的含量较低，变化范围分别为0.02%～0.11%和0.01%～0.08%。元素面扫描结果表明：Co含量较高的部位与镍黄铁矿范围完全一致，说明Co主要赋存于镍黄铁矿中。金川矿床整体Co/Ni平均值为0.042，与全球典型橄榄岩相地幔Co/Ni值（0.055）相似，表明其岩浆源区主要为橄榄岩相。高程度的部分熔融可能是导致其母岩浆中Co绝对含量较高，但Co/Ni值相对较低的原因之一。硫化物熔离时，Co更倾向于进入硫化物；但相对于Ni，进入硫化物的Co较少，导致不同矿石类型之间S含量与Co/Ni值之间呈明显的负相关性。硫化物分离结晶作用进一步促使Co向镍黄铁矿中富集。
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关键词:
- Co的赋存状态 /
- 分配系数 /
- 富集过程 /
- 金川超大型铜镍矿 /
- 龙首山隆起带 /
- 甘肃
Abstract:As the largest Ni–Co (PGE) magmatic sulfide deposit in China, the Jinchuan is located in the eastern segment of Longshoushan terrane. The most important sulfide assemblages are pyrrhotite, pentlandite, and chalcopyrite. A small account of independent cobalt minerals, such as cobaltite occurrences mainly in the disseminated ores. The whole rock analytical results show a good positive relationship between Co and S, Ni, but have no correlation with As. The Co/Ni ratio decrease with the increase of sulfide content. Based on the EMPA data of sulfide minerals. The cobalt content of pentlandite arranges from 0.32 to 1.93% and the average value is 0.81%, which is much bigger than the cobalt content in pyrrhotite (0.02%～0.11%) and chalcopyrite (0.01%～0.08%). The EPMA map of chalcophile elements also shows that the area of high cobalt content is completely consistent with the pentlandite, indicating that cobalt mainly occurs in the pentlandite. The average Co/Ni ratio of the Jinchuan deposit is 0.042, which is almost equal to the typical peridotite mantle (0.055), implying that the primitive magma of Jinchuan derived from the peridotite mantle. Compared to the typical basalt, the Co/Ni ratio of the Jinchuan deposit is much lower, and litter lower than the picrite, which indicates that a high degree of partial melting occurred in the mantle source. During the sulfide segregation, the cobalt mainly migrates to the sulfide melt, but the cobalt content is less than nickel content, causing the negative correlation between the S and Co/Ni. The fractional crystallization of sulfide melt further promotes the enrichment of cobalt into pentlandite.
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Key words:
- occurrence state of cobalt /
- partition coefficient /
- enrichment process /
- Jinchuan giant Ni–Cu deposit /
- Longshoushan terrane /
- Gansu
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图 1 金川铜镍矿床大地构造位置（a）及龙首山隆起带区域地质简图（b）（据 Duan et al.，2016修改）
Figure 1.
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图 2 金川矿床矿区地质简图（a）、矿床纵投影图（b）及典型勘探线剖面图（c）
Figure 2.
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图 3 金川矿床磁黄铁矿与镍黄铁矿产状特征
Figure 3.
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图 4 S、Ni、Cu及As元素与Co和Co/Ni的相关性图解
Figure 4.
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图 5 金川矿床不同矿石类型及产状磁黄铁矿Fe原子比与Ni、Co含量图解
Figure 5.
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图 6 金川矿床镍黄铁矿中各元素含量及元素比值相关性图解
Figure 6.
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图 7 黄铜矿、方黄铜矿Cu–Ni（a）和Cu–Co（b）的相关性图解
Figure 7.
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图 8 金川矿床硫化物电子探针元素面扫描
Figure 8.
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图 9 硫化物分离结晶过程中Co、Ni等亲铜元素的富集过程示意图（据 Chen et al.，2015 ； Helmy et al.，2021修改）
Figure 9.
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表 1 金川矿床全岩Ni、Co、Cu、S等元素含量（%）
Table 1. The Ni, Co, Cu, and S contents (%) of the ores in the Jinchuan deposit
样品编号 矿石类型 矿体编号 S Co Cu Ni As ZK-4-5-1 浸染状矿化 24号矿体 2.38 0.02 0.16 0.53 1.57 ZK-4-5-2 稠密浸染状矿化 10.52 0.05 2.15 2.98 1.90 ZK-4-5-5 稠密浸染状矿化 9.12 0.02 5.45 0.94 1.75 ZK-4-5-7 稠密浸染状矿化 11.71 0.06 1.06 2.74 1.22 ZK-4-5-9 稠密浸染状矿化 7.84 0.03 4.36 1.43 4.11 ZK-4-5-12 稠密浸染状矿化 3.89 0.02 1.69 1.18 4.06 ZK-4-5-15 稠密浸染状矿化 9.36 0.06 1.76 3.16 1.90 ZK-4-5-17 稠密浸染状矿化 9.10 0.06 1.84 3.07 1.25 ZK-4-5-19 稠密浸染状矿化 4.08 0.03 0.27 1.35 2.53 ZK-4-5-21 浸染状矿化 1.52 0.02 0.25 0.37 2.30 ZK-4-5-22 星点状矿化 0.22 0.01 0.04 0.10 1.18 ZK-4-5-23 星点状矿化 0.96 0.01 0.16 0.25 2.05 ZK-4-5-24 星点状矿化 0.26 0.01 0.02 0.11 1.52 ZK12-5-1 岩石 1号矿体 0.01 0.00 0.00 0.00 0.42 ZK12-5-5 岩石 0.10 0.01 0.01 0.09 1.20 ZK12-5-6 岩石 0.24 0.01 0.06 0.12 2.15 ZK12-5-7 星点状矿化 0.85 0.01 0.08 0.24 1.41 ZK12-5-8 浸染状 2.06 0.02 0.13 0.52 1.87 ZK12-5-9 浸染状 1.92 0.02 0.54 0.43 1.69 ZK12-5-10 浸染状 5.66 0.04 1.42 1.33 1.85 ZK12-5-11 浸染状 1.21 0.01 0.09 0.34 1.17 ZK12-5-12 浸染状 3.53 0.02 0.17 0.83 1.56 ZK12-5-15 稠密浸染状矿化 5.85 0.04 0.49 1.33 3.10 ZK12-5-16 稠密浸染状矿化 7.33 0.04 0.47 1.56 1.99 ZK12-5-21 稠密浸染状矿化 9.31 0.05 1.91 1.75 0.29 ZK12-5-23 稠密浸染状矿化 8.22 0.05 0.52 1.97 3.34 ZK12-5-26 稠密浸染状矿化 8.93 0.05 1.07 2.00 1.31 ZK12-5-30 稠密浸染状矿化 8.61 0.04 0.30 1.51 0.22 ZK12-5-34 稠密浸染状矿化 8.39 0.04 1.52 2.01 2.84 ZK12-5-35 星点状矿化 0.93 0.01 0.13 0.21 1.55 ZK12-5-36 浸染状 3.42 0.01 0.56 0.52 1.99 ZK16-2-4 岩石 2号矿体 0.09 0.01 0.00 0.12 0.85 ZK16-2-6 岩石 0.07 0.01 0.00 0.10 0.44 ZK16-2-8 岩石 0.04 0.01 0.01 0.09 0.57 ZK16-2-9 星点状矿化 0.22 0.01 0.04 0.13 0.44 ZK16-2-10 星点状矿化 0.28 0.01 0.03 0.20 0.80 ZK16-2-12 星点状矿化 0.30 0.01 0.03 0.19 0.72 ZK16-2-14 浸染状 1.20 0.01 0.11 0.42 2.58 ZK16-2-15 浸染状 2.81 0.02 0.17 0.54 0.41 ZK16-2-19 星点状矿化 0.62 0.01 0.12 0.19 0.34 ZK16-2-23 星点状矿化 0.62 0.01 0.04 0.18 0.67 ZK16-2-30 浸染状 2.30 0.02 0.71 0.39 0.69 ZK16-2-32 浸染状 2.01 0.02 0.16 0.46 0.62 ZK16-2-34 浸染状 2.56 0.02 0.16 0.58 0.83 ZK16-2-39 浸染状 2.44 0.02 0.52 0.47 0.52 ZK16-2-40 浸染状 2.82 0.02 0.17 0.58 5.31
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表 2 磁黄铁矿电子探针分析结果（%）
Table 2. The EPMA result (%) of pyrrhotite in the Jinchuan deposit
钻孔编号 矿体编号 矿石类型 种属 矿物特征 Fe Ni Co S Total Fe（原子比） zk4-5 24号矿体 星点状 六方 Po≈Pn 60.92 0.02 0.05 38.40 99.45 47.58 六方 Po≈Pn 60.49 – 0.06 38.72 99.32 47.21 六方 Po≈Pn 60.77 – 0.07 38.59 99.46 47.41 六方 Po≈Pn 62.45 – 0.06 36.80 99.32 49.28 六方 Po≈Pn 60.81 0.04 0.05 38.83 99.75 47.26 海绵陨铁状 单斜 Po≈Pn 59.97 0.14 0.05 39.24 99.42 46.62 单斜 Po≈Pn 59.41 0.07 0.07 39.49 99.09 46.24 单斜 Po≈Pn 59.75 0.19 0.06 39.66 99.68 46.24 单斜 Po≈Pn 59.77 0.05 0.08 39.53 99.48 46.37 六方 Po≈Pn 60.61 – 0.06 38.81 99.52 47.20 单斜 Po＜Pn 59.49 0.20 0.04 38.99 98.78 46.56 单斜 Po＜Pn 59.18 0.18 0.07 39.18 98.67 46.31 单斜 Po＜Pn 59.95 0.16 0.08 39.55 99.85 46.39 zk12-5 1号矿体 星点状 陨硫铁 Po＞Pn 62.75 – 0.08 36.23 99.07 49.78 陨硫铁 Po＞Pn 63.45 – 0.08 36.36 99.97 49.96 六方 Po 61.49 – 0.04 36.61 99.45 48.59 六方 Po 62.98 – 0.08 36.89 100.25 49.34 陨硫铁 Po≈Pn 63.62 – 0.06 36.45 100.29 49.97 陨硫铁 Po≈Pn 63.69 0.03 0.08 36.36 100.19 50.05 陨硫铁 Po≈Pn 62.74 – 0.07 36.15 99.01 49.83 陨硫铁 Po≈Pn 63.32 – 0.05 36.36 99.83 49.93 陨硫铁 Po≈Pn 63.21 0.02 0.05 36.45 99.84 49.81 六方 Po≈Pn 62.89 0.02 0.08 36.43 99.46 49.69 浸染状 六方 Po＞Pn 62.90 0.01 0.06 36.47 99.54 49.67 六方 Po＞Pn 62.76 – 0.11 36.54 99.45 49.55 陨硫铁 Po＞Pn 63.28 0.03 0.07 36.46 99.92 49.82 陨硫铁 Po＞Pn 63.30 – 0.09 36.57 100.03 49.76 陨硫铁 Po＞Pn 63.18 0.02 0.06 36.24 99.51 49.94 海绵陨铁状 陨硫铁 Po≈Pn 62.98 0.02 0.08 36.16 99.30 49.90 陨硫铁 Po≈Pn 63.29 – 0.09 36.39 99.91 49.88 陨硫铁 Po≈Pn 62.87 – 0.06 36.25 99.22 49.82 陨硫铁 Po≈Pn 63.18 – 0.11 36.50 99.91 49.75 陨硫铁 Po≈Pn 63.30 – 0.09 36.42 99.83 49.86 陨硫铁 Po≈Pn 63.11 – 0.05 36.44 99.68 49.79 六方 Po≈Pn 63.09 0.03 0.11 36.85 100.12 49.47 六方 Po≈Pn 62.91 – 0.07 36.48 99.53 49.67 六方 Po≈Pn 62.72 – 0.06 36.34 99.13 49.70 六方 Po≈Pn 62.75 – 0.07 36.51 99.37 49.59 六方 Po≈Pn 62.78 – 0.09 36.63 99.55 49.51 六方 Po≈Pn 63.02 – 0.08 36.72 99.90 49.55 六方 Po≈Pn 63.05 0.01 0.08 36.68 99.85 49.58 六方 Po≈Pn 63.20 – 0.02 36.58 99.84 49.73
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续表2 钻孔编号 矿体编号 矿石类型 种属 矿物特征 Fe Ni Co S Total Fe（原子比） zk12-5 1号矿体 海绵陨铁状 六方 Po≈Pn 62.72 – 0.04 36.42 99.22 49.64 六方 Po≈Pn 62.46 – 0.07 36.54 99.12 49.45 六方 Po≈Pn 62.87 – 0.06 36.49 99.54 49.65 陨硫铁 Po＜Pn 63.41 – 0.07 36.58 100.15 49.80 陨硫铁 Po＜Pn 63.88 0.01 0.06 36.48 100.52 50.05 陨硫铁 Po＜Pn 63.26 – 0.08 36.42 99.78 49.85 陨硫铁 Po＞Pn 63.44 0.01 0.09 36.52 100.09 49.84 陨硫铁 Po＞Pn 63.88 0.01 0.10 36.33 100.39 50.14 六方 Po＜Pn 63.46 0.01 0.05 36.72 100.26 49.74 六方 Po＞Pn 61.14 0.09 0.08 38.58 99.95 47.52 六方 Po＞Pn 62.01 0.07 0.07 37.95 100.11 48.30 六方 Po＞Pn 60.71 0.09 0.07 38.32 99.25 47.52 六方 Po＞Pn 60.99 0.12 0.07 38.41 99.64 47.57 六方 Po＞Pn 61.82 0.09 0.06 37.94 100.04 48.23 单斜 Po 60.19 0.25 0.10 38.85 99.41 46.90 单斜 Po 60.04 0.26 0.09 38.84 99.24 46.85 单斜 Po 60.42 0.31 0.06 39.28 100.17 46.71 单斜 Po 60.13 0.14 0.09 39.36 99.75 46.59 单斜 Po＞Pn 59.95 0.12 0.09 39.19 99.47 46.63 单斜 Po＞Pn 59.91 0.12 0.07 39.64 99.80 46.33 单斜 Po＞Pn 60.11 0.13 0.09 39.61 99.98 46.43 单斜 Po＞Pn 59.80 0.16 0.04 39.24 99.27 46.54 zk16-2 2号矿体 浸染状 六方 Po＞Pn 63.13 – 0.04 36.77 100.10 49.57 六方 Po＞Pn 62.87 – 0.09 37.18 100.21 49.17 单斜 Po≈Pn 60.19 0.03 0.07 39.63 100.05 46.48 单斜 Po≈Pn 60.16 0.31 0.07 39.58 100.18 46.42 单斜 Po≈Pn 59.75 0.06 0.08 39.58 99.49 46.34 六方 Po≈Pn 61.08 – 0.06 38.75 99.89 47.43 六方 Po≈Pn 60.83 – 0.07 38.94 99.88 47.21 六方 Po≈Pn 61.28 0.01 0.05 39.17 100.53 47.25 单斜 Po≈Pn 59.80 0.12 0.07 39.38 99.42 46.46 单斜 Po＞Pn 59.91 0.28 0.08 39.63 99.99 46.27 陨硫铁 Po＞Pn 63.22 0.02 0.10 36.41 99.76 49.82 六方 Po＞Pn 61.62 0.02 0.08 38.65 100.44 47.70 六方 Po＞Pn 61.10 – 0.07 38.44 99.63 47.64 注：“–”表示低于检测线0.01%。
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表 3 镍黄铁矿电子探针分析结果（%）
Table 3. The EPMA results (%) of pentlandite in the Jinchuan deposit
钻孔编号 矿体 矿石类型 矿物特征 Fe Ni Co Cu Te S Total zk4-5 24号矿体 星点状 Po≈Pn 31.28 33.74 0.88 0.03 0.81 32.95 99.75 Po≈Pn 31.22 34.11 0.98 0.01 0.78 33.20 100.32 Po≈Pn 32.92 31.29 0.87 0.77 0.70 33.37 99.93 Po＜Pn 33.10 32.21 1.05 0.02 0.65 32.47 99.52 Po＜Pn 31.97 33.60 1.03 0.03 0.30 33.11 100.14 海绵陨铁状 Po≈Pn 31.21 32.60 0.47 1.15 0.69 33.54 99.66 Po≈Pn 35.33 29.04 0.32 0.18 0.26 34.07 99.21 Po≈Pn 30.29 36.00 0.47 0.05 0.33 33.22 100.40 Po≈Pn 31.23 32.98 0.52 1.81 0.72 33.65 100.96 Po≈Pn 31.32 34.65 0.49 0.16 0.28 33.08 100.01 Po≈Pn 30.19 35.28 0.57 0.21 0.83 33.19 100.33 Po＜Pn 32.22 33.61 0.40 0.16 0.28 33.41 100.14 Po＜Pn 31.36 34.37 0.50 0.04 0.30 33.79 100.35 Po＜Pn 31.44 34.09 0.38 0.08 0.29 33.23 99.54 Pn 38.92 26.99 0.33 – 0.58 31.98 98.81 Pn 41.27 23.56 0.44 0.31 0.24 33.04 98.95 Pn 41.19 22.44 0.41 0.73 0.54 33.99 99.32
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续表3 钻孔编号 矿体 矿石类型 矿物特征 Fe Ni Co Cu Te S Total zk12-5 1号矿体 星点状 Po≈Pn 32.97 32.58 0.88 0.00 0.75 32.80 100.02 Po≈Pn 33.05 32.53 0.85 0.03 0.70 33.17 100.38 Po≈Pn 32.97 32.98 0.88 0.06 0.79 33.18 100.88 Po≈Pn 33.85 32.08 0.83 0.04 0.66 32.98 100.46 Po≈Pn 33.17 32.65 0.92 0.01 0.27 32.93 100.00 Po≈Pn 33.39 32.36 0.86 0.02 0.78 33.31 100.79 Po＞Pn 35.06 29.83 1.32 0.04 0.29 33.28 99.87 Po＞Pn 34.84 29.76 1.91 0.03 0.72 33.35 100.69 Po＞Pn 35.63 29.48 1.87 0.02 0.75 32.98 100.78 Po＞Pn 35.10 29.75 1.42 0.02 0.24 33.37 99.92 浸染状 Po＞Pn 34.41 31.30 0.86 0.01 0.25 32.95 99.79 Po＞Pn 34.90 30.93 0.85 0.02 0.30 33.25 100.31 海绵陨铁状 Po＜Pn 33.07 32.66 0.74 0.01 0.30 33.07 99.89 Po＜Pn 33.51 32.78 0.78 0.02 0.76 33.14 101.02 Pn 32.98 33.23 0.77 0.01 0.30 33.09 100.38 Pn 35.72 30.85 0.77 0.07 0.71 33.56 101.73 Pn 33.47 32.97 0.78 0.10 0.27 33.13 100.77 Pn 33.47 32.15 0.74 0.03 0.26 33.41 100.09 Po＞Pn 32.94 31.24 0.65 0.03 0.26 32.94 98.16 Po＞Pn 33.24 31.98 0.62 0.06 0.76 33.01 99.68 Po＞Pn 33.26 32.26 0.70 0.02 0.68 33.18 100.14 Po＞Pn 33.12 32.88 0.62 – 0.72 33.09 100.50 Po＞Pn 33.38 32.70 0.66 0.01 0.68 32.97 100.43 Po＞Pn 32.82 32.35 0.67 0.01 0.29 33.88 100.07 Po＞Pn 33.01 32.26 0.68 0.01 0.26 32.85 99.08 Po＞Pn 32.82 32.60 0.67 0.02 0.78 33.44 100.39 Po＞Pn 33.02 32.44 0.68 0.04 0.26 32.98 99.43 Po＞Pn 32.48 32.18 0.68 0.01 0.77 33.33 99.52 Po＞Pn 32.58 32.53 0.74 – 0.31 33.36 99.56 Po＞Pn 32.63 32.61 0.72 0.03 0.75 33.30 100.06 Po＞Pn 32.43 32.54 0.71 – 0.67 33.14 99.51 Po＞Pn 33.93 32.14 0.64 0.06 0.74 33.34 100.86 Po＞Pn 34.03 31.61 0.63 0.04 0.70 33.33 100.41 Po＞Pn 33.64 31.80 0.60 0.05 0.67 33.15 99.91 Po＞Pn 33.46 31.82 0.65 0.03 0.26 33.32 99.55 Po＞Pn 33.98 32.23 0.68 0.02 0.77 33.34 101.05 Po＞Pn 32.19 33.41 0.87 0.03 0.29 33.00 99.84 Po＞Pn 31.75 32.98 0.83 0.01 0.27 32.83 98.81 Po＞Pn 31.90 33.57 0.85 0.04 0.84 33.65 100.91 Po＞Pn 30.97 34.37 0.82 0.03 0.82 33.07 100.11 Po＞Pn 31.36 34.21 0.81 0.02 0.76 33.15 100.34 Po＞Pn 33.60 32.83 0.73 0.01 0.79 33.47 101.52 Po＞Pn 33.40 32.63 0.90 0.10 0.26 33.49 100.82 zk16-2 2号矿体 浸染状 Po≈Pn 30.57 34.12 0.71 0.07 0.77 33.42 99.68 Po≈Pn 31.93 33.72 1.26 0.18 0.82 33.06 100.98 Po≈Pn 34.44 31.29 1.75 0.31 0.26 33.45 101.57 Po≈Pn 29.04 36.47 0.97 0.14 0.30 33.27 100.27 Po≈Pn 29.99 35.84 1.09 0.16 0.32 33.11 100.54 Po＞Pn 28.84 38.02 0.41 0.03 0.32 33.21 100.86 Po＞Pn 30.04 35.48 0.99 0.05 0.32 33.35 100.26 Po＞Pn 30.54 35.63 0.80 0.05 0.29 33.22 100.60 Po＞Pn 28.86 36.31 1.93 0.05 0.31 33.00 100.49 Po＞Pn 28.08 38.17 0.65 0.22 0.31 33.45 100.90 注：“–”表示低于检测限。
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表 4 黄铜矿和方黄铜矿矿电子探针分析结果（%）
Table 4. The EPMA result (%) of chalcopyrite and cubanite in the Jinchuan deposit
钻孔编号 矿体编号 矿石类型 矿物种属 Fe Cu Ni Co S Total zk4-5 24号矿体 星点状 Cb 41.01 23.82 0.01 0.06 35.04 99.99 Cb 41.16 23.50 – 0.04 35.09 99.83 Ccp 30.35 34.70 – 0.02 34.29 99.37 海绵陨铁状 Cb 41.76 22.46 0.01 0.06 35.28 99.64 Cb 41.07 23.39 0.09 0.03 35.38 100.01 Cb 44.01 18.30 0.80 0.08 35.09 98.31 zk12-5 1号矿体 星点状矿石 Ccp 30.81 34.85 – 0.07 34.88 100.65 浸染状矿石 Ccp 30.65 35.10 – 0.03 34.72 100.57 Ccp 30.50 35.03 – 0.04 34.77 100.34 海绵陨铁状 Ccp 30.26 33.97 0.35 0.05 35.15 99.82 Ccp 30.17 34.52 0.15 0.04 34.98 99.90 Ccp 30.04 34.75 0.01 0.04 34.45 99.39 Ccp 30.60 35.16 – 0.02 34.87 100.65 Ccp 30.16 34.55 – 0.03 35.20 100.01 Ccp 30.62 33.95 0.01 0.01 33.89 98.54 Ccp 30.70 34.53 – 0.01 34.75 100.06 Ccp 31.13 34.40 0.02 0.03 34.71 100.30 zk16-2 2号矿体 星点状矿化 Cb 42.86 20.62 0.23 0.05 34.61 98.40 浸染状矿石 Cb 41.03 23.64 0.07 0.06 34.88 99.70 注：“–”表示低于检测限。
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