Occurrence and geochemical characteristics of cobalt of the Poyi nickel deposit in the Beishan region, Xinjiang: Insights into cobalt mineralization
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摘要:
钴作为当今社会必需的一种关键矿产资源, 岩浆铜镍矿床是我国钴资源供应的重要矿床种类之一, 该类矿床中钴元素通常赋存于镁铁质硅酸盐矿物、硫化物、类硫化物和铁氧化物中, 然而镁铁质硅酸盐和铁氧化物中的钴难以分选利用, 因此钴赋存状态的厘定是铜镍矿床中钴资源评价和利用的重要前提。新疆东天山-北山地区发育大量晚古生代、普遍伴生钴的岩浆铜镍矿床, 其中位于北山地区的坡一镍矿床以赋含高镍硫化物为特色, 是研究岩浆铜镍矿床中钴元素的赋存状态、分布特征以及钴与镍相互关系的理想对象。坡一镍矿的含矿岩相主要为单辉橄榄岩、纯橄岩和橄长岩, 以稀疏浸染状矿化为主, 钴主要以类质同象形式赋存于镍黄铁矿, 其次为铬尖晶石、橄榄石和磁黄铁矿, 少见独立钴矿物。矿物微区原位分析结果显示原生矿物中钴含量由高到低依次为镍黄铁矿(~8404×10-6)>>铬尖晶石(~475×10-6)>磁黄铁矿(高Ni含量)(~299×10-6)>橄榄石(~137×10-6)>黄铜矿(~13.0×10-6)>磁黄铁矿(低Ni含量)(~8.35×10-6)。坡一岩体的蚀变橄榄岩中发育三种产状的次生磁铁矿: 蚀变橄榄石裂理中细脉状磁铁矿、铬尖晶石边部环状磁铁矿边、硫化物矿边部和裂隙中次生磁铁矿边。元素面扫描结果显示次生磁铁矿中Co含量明显高于原生硫化物、氧化物和硅酸盐矿物, 且显示富Co贫Ni特征。坡一矿床中硫化物和硅酸盐矿物表现出明显的Co-Ni正相关, 而铬尖晶石中Co和Ni显示负相关, 表明Co2+主要以类质同象形式替代Fe2+进入硫化物和硅酸盐矿物晶格, 以替代Fe2+、Ni2+的形式进入铬尖晶石。坡一矿床中Ni和Co的共生行为, 主要归因于岩浆演化过程硫化物熔离和硅酸盐矿物分离结晶过程中相近的配分行为, 而Ni和Co的离散特征主要受控于铬尖晶石的分离结晶和R值(岩浆和硫化物质量比)的变化、热液蚀变过程中次生磁铁矿Co富集作用。由于铬尖晶石与硅酸盐矿物中的钴难以分选利用, 北山地区的钴矿资源勘查应关注贫铬尖晶石、橄榄石镍亏损的富硫化物超镁铁质岩体。
Abstract:As a critical mineral, cobalt has a wide range of applications in battery manufacturing, aerospace and medical fields in today's world. Magmatic Ni-Cu sulfide deposit is one of the most important cobalt sources in China. Cobalt in Ni-Cu deposits can be contained in various minerals such as mafic silicate minerals, sulfides, sulfide-like minerals and iron oxides. However, cobalt in mafic silicates and iron oxides is difficult to separate. Therefore, the determination of cobalt occurrence is important for evaluating and utilizing cobalt resources in Ni-Cu deposits. A large number of Late Paleozoic magmatic Ni-Cu sulfide deposits are developed in the East Tianshan-Beishan region of Xinjiang, in which cobalt commonly exists as an associated product. The Poyi magmatic nickel deposit is located in the Beishan region of the southern Central Asian Orogenic Belt, and is characterized by high-Ni tenor sulfides, making it is an ideal deposit to investigate the occurrence and distribution of cobalt in magmatic sulfide deposits, and the relationship between cobalt and nickel. The Poyi deposit is hosted in a small ultramafic body (mainly wehrlite and dunite) which contains disseminated sulfide mineralization. Cobalt mainly occurs in pentlandite in isomorphic state, followed by chrome spinel, olivine and pyrrhotite. Cobalt mineral is rare in this deposit. The LA-ICP-MS analyses results show that the sequence of concentrations of cobalt in the primary minerals is pentlandite (~8404×10-6)>>Cr-spinel (~475×10-6)>pyrrhotite (high Ni) (~299×10-6)>olivine (~137×10-6)>chalcopyrite (~13.0×10-6)>pyrrhotite (low Ni) (~8.35×10-6). Three types of secondary magnetite are recognized in the altered ultramafic rocks: veinlet magnetite in the altered olivine fracture, ring-shaped magnetite at the edge of the Cr-spinel, and irregular magnetite at the edge of sulfides. Elemental scanning results show that the secondary magnetite is rich in Co and depleted in Ni, and its Co concentration is much higher than those of primary sulfide, oxide and silicate minerals. The sulfide and silicate minerals show positive Ni-Co correlations, while Co and Ni in the Cr-spinel show a negative correlation, indicating that Co2+ enters the sulfide and silicate mineral lattice mainly by replacing Fe2+, and enters the Cr-spinel by replacing Fe2+ and Ni2+. The consistent behavior of Ni and Co in the Poyi deposit is mainly attributed to the similar partitioning behavior during sulfide segregation and crystallization of silicates, while the discrete characteristics of Ni and Co are mainly controlled by fractional crystallization of spinel and variations of R factor (the ratio of silicate magma to sulfide melt), and Co enrichment in secondary magnetite during hydrothermal alternation. Since cobalt in spinel oxides and silicate minerals is difficult to separate and utilize, the selection of cobalt ore resources in the Beishan region should focus on sulfide-rich intrusions with low proportion of Cr-spinel and low Ni olivine.
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Key words:
- Co-and Ni-bearing minerals /
- Occurrence /
- Co mineralization /
- Poyi deposit /
- Beishan
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图 1
中亚造山带南缘北山地区地质简图(据Xiao et al., 2004修改)
Figure 1.
Simplified geologic map of the Beishan region in the southern Central Asian Orogenic Belt (CAOB) (modified after Xiao et al., 2004)
图 2
北山坡北地区二叠纪镁铁-超镁铁质岩分布图(a)、坡一镁铁-超镁铁质岩体地质图(b)及其勘探线剖面图(c)(据Xue et al., 2016修改)
Figure 2.
Distribution map of Permian mafic-ultramafic rocks in the Pobei area (a), geological map (b) and cross section of the prospecting line (c) of the Poyi mafic-ultramafic complex (modified after Xue et al., 2016)
图 3
坡一岩体矿化超镁铁质岩相正交偏光显微照片(a-c)和背散射电子图像(d)
Figure 3.
Photomicrographs (a-c) and back-scattered electron images (d) of mineralized ultramafic rocks of Poyi
图 4
坡一矿化岩体中金属硫化物和氧化物反射光显微照片(a, f)和背散射电子图像(b-e)
Figure 4.
Photomicrographs (a, f) and back-scattered electron images (b-e) of mineralized related sulfide minerals
图 5
坡一矿床单辉橄榄岩(样品ZK22-4-1030)矿物自动化定量分析照片
Figure 5.
TIMA images of wehrlite (Sample ZK22-4-1030) of the Poyi deposit
图 6
坡一岩体纯橄岩(样品ZK22-4-893)矿物自动化定量分析照片
Figure 6.
TIMA images of dunite (Sample ZK22-4-893) of the Poyi deposit
图 7
坡一矿床矿石中原生硫化物和次生磁铁矿矿物自动化定量分析照片
Figure 7.
TIMA images of co-located primary sulfide mineral and secondary magnetite in the Poyi deposit
图 8
坡一矿床矿石的硫、镍、铜和钴元素相关性图解
Figure 8.
Correlation diagrams of S, Ni, Cu and Co of the sulfide ores in the Poyi deposit
图 9
坡一矿床矿石中硫化物、硅酸盐矿物和尖晶石氧化物的镍、铁和钴元素相关性图解
Figure 9.
Correlation diagrams of Ni, Fe and Co of the sulfide ores, silicate mineral and spinel oxides in the Poyi deposit
图 10
坡一矿床矿化超镁铁质岩相矿物质量比例图
Figure 10.
Diagrams of mineral proportion of mineralized ultramafic rocks in the Poyi deposit
表 1
坡一矿床矿化超镁铁质岩中硫、镍、铜和钴(wt%)组成
Table 1.
Concentrations of S, Ni, Cu and Co (wt%) of the sulfide-mineralized ultramafic rocks in the Poyi deposit
样品号 岩性 S Ni Cu Co PY23-2-760.5* 纯橄岩 1.37 0.96 0.29 0.019 ZK23-3-1124 0.11 0.25 0.01 0.013 ZK23-3-1193.5 0.06 0.26 0.01 0.013 ZK23-3-1273 0.04 0.25 0.01 0.013 ZK23-3-1360 0.06 0.25 0.01 0.014 PY23-2-446 单辉橄榄岩 0.06 0.25 0.01 0.012 PY23-2-493 0.04 0.23 0.01 0.013 PY23-2-539.2* 0.37 0.4 0.07 0.016 PY23-2-551.7 0.13 0.25 0.05 0.016 PY23-2-795.6 0.22 0.29 0.07 0.013 PY23-2-844 0.12 0.19 0.03 0.014 PY23-2-868.2 0.13 0.19 0.03 0.015 PY23-3-772* 0.34 0.34 0.08 0.016 PY23-3-790* 0.68 0.52 0.15 0.019 PY23-3-817.5* 0.46 0.33 0.10 0.018 PY23-3-882 0.69 0.43 0.13 0.019 PY23-3-886* 0.69 0.25 0.13 0.019 PY23-3-948.6 0.22 0.35 0.07 0.013 PY23-3-1057* 1.01 0.57 0.23 0.018 PY27-5-643.7 0.05 0.26 0.01 0.013 PY27-5-821 0.05 0.27 0.01 0.013 PY23-3-589 0.09 0.28 0.02 0.015 PY23-2-894.5 0.52 0.34 0.09 0.019 PY23-3-846 0.13 0.22 0.03 0.015 PY23-2-728.5 橄长岩 0.05 0.29 0.01 0.013 PY23-2-742 0.05 0.29 0.01 0.013 PY23-2-746* 0.63 0.54 0.16 0.014 PY23-3-761* 0.92 0.7 0.24 0.018 PY23-3-874.5* 0.44 0.23 0.06 0.010 ZK26-4-572.8 橄榄辉长岩 0.10 0.06 0.01 0.008 ZK38-3-774 0.03 0.06 0.01 0.008 PYC-11 0.12 0.04 0.01 0.006 PYC-14 0.19 0.04 0.01 0.006 PYC-15 0.11 0.06 0.03 0.006 PYG-1 辉长岩 0.04 0.01 0.00 0.002 PYG-5 0.05 0.03 0.01 0.003 注：*样品的S、Ni、Cu含量引自 Xue et al. (2016) 
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表 2
坡一矿床矿石中硫化物的主量和微量元素组成(×10-6)
Table 2.
Major and trace element compositions of the sulfides in the Poyi deposit (×10-6)
样品号 岩性 矿物 S Co Ni Cu Cr As Se Te Bi ZK224-803-12 单辉橄榄岩 黄铜矿 411497 0.08 5751 350551 15.3 0.01 115 30.8 4.31 ZK224-803-13 单辉橄榄岩 417535 0.15 3555 338492 3.36 0.00 116 30.4 0.54 ZK224-803-14 单辉橄榄岩 398491 0.11 5104 350078 6.22 0.00 104 35.9 1.25 ZK224-893-11 纯橄岩 408316 0.04 377 383262 1.09 0.00 101 18.4 24.6 ZK224-893-12 纯橄岩 389812 0.03 438 386243 0.97 0.00 102 22.8 24.5 ZK224-893-13 纯橄岩 412208 0.06 440 380554 1.34 0.02 103 11.6 14.8 ZK224-893-14 纯橄岩 408475 0.10 626 379771 11.8 0.03 96.3 21.4 32.6 ZK224-1030-11 单辉橄榄岩 411470 2.16 211 392313 1.77 0.00 109 29.6 0.63 ZK224-1030-12 单辉橄榄岩 422892 0.02 12.8 397112 1.20 0.05 117 22.2 23.1 ZK224-1030-13 单辉橄榄岩 416701 0.04 34.1 390073 1.16 0.00 105 15.3 24.7 ZK224-1030-14 单辉橄榄岩 210791 152 2592 208269 12.0 4.14 56.5 14.8 23.8 ZK224-1030-15 单辉橄榄岩 423931 0.18 33.3 399923 7.19 0.00 131 3.80 3.89 ZK224-803-4 单辉橄榄岩 镍黄铁矿 457955 2742 152340 5613 15.1 2.31 139 2.73 9.43 ZK224-803-6 单辉橄榄岩 309789 8290 289997 532 16.8 35.5 85.9 25.0 2.05 ZK224-803-7 单辉橄榄岩 358082 10325 395594 134 46.7 2.02 109 8.25 1.43 ZK224-803-8 单辉橄榄岩 346237 11329 379491 6813 23.3 22.7 95.3 21.9 1.57 ZK224-803-9 单辉橄榄岩 370160 10307 408915 0.94 1.39 0.81 111 1.36 0.15 ZK224-803-10 单辉橄榄岩 345138 9518 385263 259 31.1 0.15 98.9 1.40 0.51 ZK224-893-6 纯橄岩 369549 7955 437471 0.12 1.95 378 169 112 1.00 ZK224-893-7 纯橄岩 359072 4152 410891 0.22 2.28 381 143 145 0.10 ZK224-893-8 纯橄岩 338450 3777 301871 203 11.3 20.9 136 2.76 14.9 ZK224-893-9 纯橄岩 353399 3533 410595 0.16 1.09 35.4 136 4.01 3.01 ZK224-893-10 纯橄岩 352966 4931 397798 0.47 9.87 258 133 85.9 0.31 ZK224-1030-6 单辉橄榄岩 350502 10749 366903 0.04 0.96 51.6 108 65.9 0.00 ZK224-1030-7 单辉橄榄岩 320116 12229 347992 0.21 0.97 258 114 88.5 0.07 ZK224-1030-8 单辉橄榄岩 379420 12523 376388 9.22 22.8 58.0 88.4 31.0 0.15 ZK224-1030-9 单辉橄榄岩 338897 10513 361028 2.11 1.79 99.3 97.2 106 8.08 ZK224-1030-10 单辉橄榄岩 358582 11584 409873 0.05 1.38 12.4 91.8 16.0 0.01 ZK224-803-1 单辉橄榄岩 磁黄铁矿 358932 8.00 422 9.61 1.26 29.64 102 5.19 1.00 ZK224-803-2 单辉橄榄岩 394691 3.57 138 337 3.01 21.8 120 7.89 2.02 ZK224-803-3 单辉橄榄岩 384670 3.39 148 11.1 1.68 1.83 112 1.98 0.71 ZK224-803-5 单辉橄榄岩 361572 18.5 175 15.0 0.56 40.8 108 6.74 2.48 ZK224-893-1 纯橄岩 395028 10.7 4500 2.41 0.34 17.4 140 3.51 9.01 ZK224-893-2 纯橄岩 380639 6.86 1121 3.49 0.85 51.4 140 5.12 13.7 ZK224-893-3 纯橄岩 393412 5.69 3564 2.80 1.28 6.49 155 2.67 11.8 ZK224-893-4 纯橄岩 379597 0.87 122 129 2.35 9.48 138 2.72 9.65 ZK224-893-5 纯橄岩 403275 1.48 10.4 0.85 0.79 1.47 160 0.85 3.87 ZK224-1030-1 单辉橄榄岩 425638 5.38 3475 1.49 1.53 0.04 117 0.08 0.51 ZK224-1030-2 单辉橄榄岩 417895 150 7534 3.19 1.42 0.77 115 2.45 4.45 ZK224-1030-3 单辉橄榄岩 443788 491 19858 0.22 1.53 12.5 120 1.13 5.67 ZK224-1030-4 单辉橄榄岩 418492 255 6792 3.67 1.45 0.92 116 1.42 1.71 ZK224-1030-5 单辉橄榄岩 413496 27.4 4610 1.50 0.97 0.02 111 0.07 0.51
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表 3
坡一矿床矿石中硅酸盐矿物的主量和微量元素组成(×10-6)
Table 3.
Major and trace element composition of the silicate mineral in the Poyi deposit (×10-6)
样品号 岩性 矿物 Fe Co Ni Li Mg Al Ti V Cr Mn ZK224-803-1 单辉橄榄岩 橄榄石 83969 142 2292 2.62 260751 3.10 35.3 0.26 3.79 1336 ZK224-803-2 单辉橄榄岩 83789 139 2196 3.14 262885 6.07 35.5 0.49 14.9 1324 ZK224-803-3 单辉橄榄岩 82903 140 2233 2.72 262649 13.7 53.2 1.06 47.0 1328 ZK224-803-4 单辉橄榄岩 82206 141 2196 4.27 261709 5.69 53.8 0.90 20.4 1286 ZK224-803-5 单辉橄榄岩 82267 131 2268 5.80 264504 0.75 30.9 0.08 4.40 1293 ZK224-803-6 单辉橄榄岩 82907 123 1967 3.30 264518 12.2 29.3 0.26 17.5 1314 ZK224-893-1 纯橄岩 82647 129 3115 5.77 259634 31.5 93.6 1.88 37.5 1301 ZK224-893-2 纯橄岩 82143 130 3035 2.94 262293 20.1 36.3 1.26 27.4 1294 ZK224-893-3 纯橄岩 82339 134 3178 3.84 261233 5.78 50.9 0.38 5.58 1310 ZK224-893-4 纯橄岩 82776 136 3275 5.83 263483 6.41 59.8 0.76 12.0 1304 ZK224-893-5 纯橄岩 82350 134 3381 7.18 263784 1.32 54.4 0.28 12.2 1267 ZK224-893-6 纯橄岩 82551 132 3167 2.65 260876 22.8 47.4 1.97 41.8 1293 ZK224-1030-1 单辉橄榄岩 85090 140 2077 2.45 259265 49.4 56.2 1.60 119 1321 ZK224-1030-2 单辉橄榄岩 85504 140 2231 4.60 261300 2.75 52.5 0.44 20.1 1331 ZK224-1030-3 单辉橄榄岩 84905 146 2234 2.75 263257 93.0 49.1 2.32 33.3 1332 ZK224-1030-4 单辉橄榄岩 84382 149 2235 2.96 263944 1.15 27.9 0.17 5.70 1322 ZK224-1030-5 单辉橄榄岩 83856 142 2217 2.45 263801 24.0 51.9 1.28 6.93 1311 ZK224-1030-6 单辉橄榄岩 84377 133 1960 1.84 260108 29.7 21.1 0.28 14.4 1329 ZK224-803-1 单辉橄榄岩 单斜辉石 33121 38.5 628 2.53 100700 76992 8348 526 11800 428 ZK224-803-2 单辉橄榄岩 17908 21.7 314 0.74 116649 17303 1595 107 2829 275 ZK224-803-3 单辉橄榄岩 32745 36.6 573 2.60 102366 76330 8561 524 11804 436 ZK224-803-4 单辉橄榄岩 23585 25.9 429 1.97 108302 41461 3490 230 7224 307 ZK224-893-1 纯橄岩 18165 19.3 437 1.50 104401 19342 2020 172 6747 279 ZK224-893-2 纯橄岩 32799 37.2 914 2.11 102240 77728 12696 591 9495 403 ZK224-893-3 纯橄岩 32007 37.9 894 2.08 98896 74997 17418 605 11730 408 ZK224-893-4 纯橄岩 13832 13.8 241 8.20 55942 10549 2557 147 4143 450 ZK224-1030-1 单辉橄榄岩 32448 35.2 563 4.45 113355 69902 2752 210 10092 493 ZK224-1030-2 单辉橄榄岩 35361 41.3 638 4.62 104568 76946 9471 524 13704 442 ZK224-1030-3 单辉橄榄岩 35785 40.9 605 4.03 104947 77136 9639 505 13266 439 ZK224-1030-4 单辉橄榄岩 36603 39.9 629 9.48 112399 82978 1788 231 8707 634
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表 4
坡一矿床矿石中尖晶石的主量和微量元素组成(×10-6)
Table 4.
Major and trace element composition of the spinel in the Poyi deposit (×10-6)
样品号 岩性 矿物 Fe Co Ni Cu Mg Al Mn Sc Ti V Cr# ZK224-803-1 单辉橄榄岩 尖晶石 206530 479 596 7.70 68960 209223 2353 0.25 1966 1278 51.0 ZK224-803-2 单辉橄榄岩 217487 480 772 1.01 56480 163531 2573 1.71 9006 1514 51.0 ZK224-803-3 单辉橄榄岩 206576 459 1072 0.02 60680 163420 2300 2.52 7553 1465 51.0 ZK224-803-4 单辉橄榄岩 226938 531 636 0.75 60092 186255 2587 1.12 6382 1518 51.0 ZK224-803-5 单辉橄榄岩 215846 516 940 0.48 58943 170290 2560 1.46 7598 1469 51.0 ZK224-893-1 纯橄岩 218757 410 785 0.53 44033 124350 2736 1.85 9022 1843 55.2 ZK224-893-2 纯橄岩 218592 445 1153 0.00 52012 140579 2629 1.79 6750 1679 55.2 ZK224-893-3 纯橄岩 224107 437 1201 0.10 55369 128940 2677 28.6 7867 1951 55.2 ZK224-893-4 纯橄岩 223773 437 1284 53.4 48417 122821 2713 21.0 9384 1881 55.2 ZK224-893-5 纯橄岩 237789 405 1432 1.49 47169 124300 2797 29.6 9885 1900 55.2 ZK224-1030-1 单辉橄榄岩 215842 483 866 0.03 54607 148906 2653 0.84 8239 1427 51.1 ZK224-1030-2 单辉橄榄岩 234073 500 788 0.33 56805 172841 2613 0.85 4345 1396 51.1 ZK224-1030-3 单辉橄榄岩 210331 495 714 0.01 68336 201072 2329 0.96 2256 1294 51.1 ZK224-1030-4 单辉橄榄岩 214013 547 1016 0.82 63818 189266 2440 0.43 6083 1573 51.1 ZK224-1030-5 单辉橄榄岩 208793 501 925 6.02 63107 182030 2377 0.80 4942 1461 51.1 注：Cr#=Cr/(Cr+Al+Fe2+)
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