Geochemical characteristics of magnetite from Washan iron deposit in Ningwu ore district and its constraints on ore-forming
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摘要:
凹山铁矿床是一个典型的玢岩型铁矿床，成矿过程具有多阶段的特征，是宁芜矿集区凹山矿田成矿作用演化的典型代表。本次研究工作，在详细的野外地质调查研究和室内研究的基础上，将主要矿石矿物磁铁矿的形成划分为4个世代，分别为浸染状磁铁矿、角砾状磁铁矿、粗粒脉状磁铁矿和伟晶状磁铁矿，它们是四个成矿阶段的产物。电子探针和LA-ICP-MS原位分析表明，随着成矿作用的演化，磁铁矿主量元素中Ti、Mn、V含量变化微弱，Al、Mg含量增高；微量元素中Ga、Sn及高场强元素Zr、Hf、Nd、Ta含量变化较小；从角砾状矿石到伟晶状矿石Co含量逐渐增高、Sc含量逐渐降低。根据以上成矿各阶段中磁铁矿成分的变化，并结合前人研究成果得出，凹山铁矿床作为一个高温气液充填矿床，其成矿物质主要来自于岩浆演化晚期形成的高温富铁流体。在成矿过程中磁铁矿具有同源连续演化的特征，其中隐爆作用诱发了大规模铁沉淀，并为成矿提供了空间，形成了早期的浸染状和角砾状矿石；成矿过程中流体成分不断变化，后期大量挥发份的累积和外源流体的逐渐加入，形成了伟晶状矿石并使得磁铁矿具有了热液成因的特征。
Abstract:Washan iron deposit is a typical porphyry-type iron deposit, with a multi-stage ore-forming process. It displays the iron mineralization evolution of the Washan ore field. Based on the detailed field geological investigation, mineralogy and petrology study, the magnetite formation is divided into four stages, namely, disseminated magnetite, magnetite in breccia, coarse-grained vein magnetite and pegmatitic vein magnetite. In situ electron microprobe and LA-ICP-MS analysis of the magnetite from Washan iron deposit show that with the evolution of mineralization, the contents of Ti, Mn, V in magnetite are consistent; the Al and Mg contents increased; the contents of Ga, Sn and high field strength elements (Zr, Hf, Nd, Ta) change in a small range; from magnetite in breccia to pegmatitic vein magnetite, Co content gradually increased and Sc decreased gradually. The compositions of magnetite in various stages indicate that the process of magnetite mineralization has a continuous evolution with a similar source. Combined with previous studies, the mineralization formed from the iron-rich melt in the later of magmatic evolution. The large-scale iron precipitation triggered by cryptoexplosion and the corresponding breccia pipes provide available space for the mineralization. The disseminated ores and brecciated ores formed in the early stage. With the magmatic-hydrothermal evolution, magnetite showed more hydrothermal likely signature in the later stage.
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图 1
宁芜矿集区矿产地质图(据宁芜研究项目编写小组，1978)
Figure 1.
Geological map with the distribution of deposits of Ningwu ore district(after Ningwu Research Group, 1978)
图 2
凹山铁矿床剖面图(据宁芜研究项目编写小组，1978)
Figure 2.
Section of the Washan iron deposit with mineralization in Ningwu basin (after Ningwu Research Group, 1978)
图 5
凹山铁矿床各阶段磁铁矿主量元素成分特征
Figure 5.
Compositions of major elements from various stages of magnetite in Washan iron deposit
图 6
凹山铁矿床磁铁矿LA-ICP-MS微量元素测试值及仪器检测限对照蛛网图
Figure 6.
LA-ICP-MS analytical results from magnetite of Washan iron deposit, which are compared to the instrument limits of detection
图 7
磁铁矿LA-ICP-MS测试过程中典型电感耦合等离子质谱输出信号图谱
Figure 7.
Typical ICP-MS counts output for magnetite analysis by laser ablation
图 8
凹山铁矿床磁铁矿微量元素特征
Figure 8.
Compositions of trace elements from various stages of magnetite in Washan iron deposit
图 9
磁铁矿TiO2-Al2O3-(MgO+MnO)成因分类图解(据林师整，1982)
Figure 9.
TiO2-Al2O3-(MgO+MnO)magnetite genetic classification diagram (after Lin et al., 1982)
图 10
磁铁矿(Ca+Al+Mn)-(Ti+V)成因分类图解(底图据Dupuis and Beaudoin, 2011)
Figure 10.
(Ca+Al+Mn)-(Ti+V)magnetite genetic classification diagram (after Dupuis and Beaudoin, 2011)
表 1
凹山铁矿床磁铁矿电子探针测试成分特征表(wt%)
Table 1.
Major element analysis (EMPA) for magnetite from Washan iron deposit (wt%)
样品号 SiO2 TiO2 Al2O3 FeO MnO MgO CaO Na2O K2O P2O5 V2O3 Total WS-2-3.2 0.22 0.03 0.00 93.17 0.00 0.00 0.00 0.00 0.00 0.01 0.00 93.18 WS-2-6 0.06 6.92 1.09 85.55 0.01 0.23 0.00 0.00 0.00 0.00 0.48 86.27 WS-2-7 0.06 2.21 1.23 89.21 0.17 1.28 0.00 0.00 0.00 0.00 0.42 91.08 WS-2-8 0.01 3.72 1.14 87.68 0.13 1.55 0.00 0.13 0.00 0.00 0.57 90.06 WS-45-4.1 0.05 2.13 1.03 89.72 0.18 0.96 0.00 0.00 0.00 0.00 0.30 91.16 WS-45-4.2 0.06 1.18 1.07 90.48 0.06 0.82 0.00 0.05 0.00 0.00 0.53 91.93 WS-45-4.3 0.07 2.09 1.22 88.79 0.00 1.29 0.00 0.02 0.00 0.03 0.47 90.60 WS-46-1.3 0.00 2.38 0.84 88.83 0.21 0.45 0.00 0.00 0.00 0.00 0.41 89.90 WS-46-2 0.03 2.00 0.89 90.09 0.07 1.07 0.00 0.00 0.02 0.00 0.63 91.87 WS-46-3 0.03 3.60 1.35 87.19 0.20 1.83 0.00 0.02 0.00 0.01 0.44 89.69 WS-46-4 0.00 2.10 1.12 89.74 0.12 0.89 0.00 0.00 0.00 0.00 0.51 91.26 WS-7-1-3.2 0.06 2.41 0.27 89.80 0.02 0.01 0.00 0.06 0.00 0.00 0.55 90.44 WS-7-1-4 0.00 1.02 0.39 92.01 0.07 0.07 0.00 0.03 0.00 0.00 0.44 92.62 WS-7-1-5.3 0.08 0.06 0.04 92.75 0.10 0.01 0.16 0.00 0.01 0.01 0.18 93.21 WS-7-2-2.2 0.03 2.42 1.15 90.05 0.40 0.03 0.01 0.00 0.00 0.00 0.35 90.83 WS-7-2-3 0.03 1.62 0.44 92.17 0.09 0.03 0.00 0.01 0.00 0.00 0.76 93.07 WS-7-2-4.2 0.03 3.13 0.35 86.61 0.33 0.00 0.00 0.57 0.09 0.00 0.54 88.13 WS-7-2-5.2 0.03 3.78 0.31 87.75 0.21 0.02 0.00 0.06 0.01 0.00 0.62 88.67 WS-7-2-6 0.00 2.33 0.36 89.94 0.10 0.00 0.00 0.33 0.02 0.00 0.32 90.71 WS-9-1-1.1 0.04 4.28 1.69 87.14 0.51 0.16 0.00 0.00 0.00 0.00 0.37 88.18 WS-9-1.2 0.05 3.64 0.29 89.51 0.44 0.06 0.00 0.00 0.00 0.01 0.67 90.69 WS-9-1-3.3 0.04 2.52 0.33 91.37 0.02 0.02 0.00 0.00 0.00 0.00 0.67 92.08 WS-44-1.1 0.12 1.68 0.63 89.34 0.06 0.36 0.11 0.07 0.00 0.01 0.59 90.52 WS-44-2.1 0.07 0.69 0.39 91.82 0.14 0.07 0.01 0.04 0.01 0.00 0.42 92.50 WS-44-4.1 0.04 3.16 0.28 89.87 0.37 0.09 0.00 0.00 0.00 0.00 0.69 91.02 WS-44-5.1 0.02 0.61 0.18 92.49 0.06 0.00 0.00 0.03 0.01 0.03 0.73 93.35 WS-44-6.2 0.78 0.62 0.32 89.79 0.00 0.25 0.16 0.15 0.00 0.00 0.67 91.02 WS-44-7.2 0.05 3.66 0.27 88.64 0.34 0.07 0.00 0.00 0.01 0.00 0.48 89.55 WS-23-1.1 0.07 4.77 0.53 89.22 0.15 0.23 0.00 0.00 0.00 0.01 0.68 90.30 WS-23-2.1 0.08 0.87 0.41 92.67 0.06 0.00 0.00 0.00 0.00 0.00 0.66 93.38 WS-23-3.2 1.58 1.69 0.23 88.51 0.03 0.00 1.32 0.21 0.00 0.00 0.52 90.58 WS-23-4.2 0.01 5.27 0.57 87.50 0.20 0.08 0.00 0.10 0.00 0.00 0.39 88.27 WS-23-8.1 0.05 3.10 1.12 88.09 0.18 0.23 0.00 0.11 0.03 0.00 0.60 89.23 WS-18-1 0.22 4.21 0.59 88.31 0.28 0.12 0.00 0.15 0.00 0.00 0.66 89.53 WS-18-2 0.10 3.50 0.83 90.07 0.00 0.12 0.00 0.01 0.00 0.00 0.58 90.78 WS-18-3 0.02 4.61 0.87 87.91 0.29 0.14 0.00 0.00 0.00 0.01 0.74 89.10 WS-8-1.1 0.04 0.81 0.23 93.09 0.12 0.02 0.00 0.02 0.00 0.00 0.45 93.70 WS-8-3 0.02 0.48 0.09 92.25 0.00 0.00 0.00 0.00 0.01 0.01 0.57 92.84 WS-8-4 0.03 3.93 0.10 89.33 0.37 0.05 0.00 0.01 0.00 0.00 0.58 90.33 WS-8-5.2 0.67 2.37 0.52 88.92 0.10 0.27 0.06 0.01 0.04 0.00 0.43 89.83 WS-16-1.3 1.27 2.48 0.44 87.08 0.06 0.11 0.69 0.69 0.03 0.00 0.31 88.97 WS-16-2.2 0.04 1.72 0.08 91.58 0.05 0.01 0.03 0.00 0.02 0.01 0.50 92.19 WS-16-3.1 0.13 0.18 0.03 93.31 0.00 0.00 0.00 0.00 0.00 0.00 0.10 93.41 WS-61-1.2 0.03 3.09 0.01 89.37 0.15 0.09 0.01 1.18 0.09 0.00 0.32 91.21 WS-61-3.2 0.21 1.05 0.00 92.88 0.12 0.07 0.09 0.01 0.00 0.00 0.09 93.25 WS-61-4.2 0.05 1.70 0.03 92.71 0.00 0.00 0.00 0.01 0.00 0.00 0.19 92.90 WS-61-5.2 0.30 0.39 0.06 91.18 0.00 0.14 0.22 0.00 0.00 0.00 0.21 91.76 WS-61-6.2 0.31 0.55 0.39 91.69 0.00 0.25 0.10 0.07 0.00 0.00 0.06 92.17 
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表 2
凹山铁矿床磁铁矿LA-ICP-MS微量元素测试成分特征表(×10-6)
Table 2.
Trace element analysis (LA-ICP-MS) for magnetite from Washan iron deposit (×10-6)
样品号 Sc Co Zn Ga Zr Nb Sn Hf Ta WS-2.1 2.441 77.33 146.8 34.38 8.024 4.835 8.679 0.2918 0.4266 WS-2-3.1 1.95 76.47 183.8 35.26 8.053 3.682 11.06 0.2928 0.3338 WS-2-4.1 2.3 90.23 146 40.53 8.127 4.694 11.6 0.2371 0.3627 WS-45-4.1 2.841 83.96 105.9 46.41 5.286 3.58 12.11 0.2294 0.4439 WS-45-4.2 2.642 84.33 126.7 47.61 4.813 3.267 10.28 0.3007 0.4093 WS-45-4.3 2.471 87.39 126.7 45.33 3.747 3.357 10.07 0.2928 0.3899 WS-46-3 2.735 88.85 153.5 41.1 5.697 4.27 9.845 0.2162 0.3651 WS-46-4 2.405 80.65 141.8 44.97 7.427 5.531 10.52 0.2535 0.3856 WS-46-8 2.459 76.59 169.6 45.07 6.67 3.65 10.45 0.2985 0.359 WS-18-1 8.805 34.04 462.2 55.54 8.159 5.618 16.41 0.343 0.4133 WS-18-2 8.598 19.84 444.1 61.58 8.653 4.991 14.2 0.583 0.29 WS-18-3 8.606 38.14 479.9 71.24 7.673 4.462 15.2 0.3494 0.3994 WS-23-1 3.946 35.08 1704 38.17 11.2 6.291 9.58 0.3142 0.478 WS-23-2 4.055 19.94 3076 32.5 8.107 5.511 8.177 0.3959 0.4554 WS-23-3 5.232 19.58 1297 36.25 6.619 5.438 9.997 0.3168 0.3407 WS-44-1 1.431 62.74 620.3 44.84 2.011 2.636 10.53 0.077 0.2147 WS-44-2 1.71 57.04 765.8 41.86 1.307 2.312 8.881 0.0787 0.1676 WS-44-3 1.252 48.84 945.7 40.83 0.7022 1.925 8.894 0.048 0.12 WS-7-1-1 6.01 15.21 209.6 40.97 2.661 2.798 11.26 0.2066 0.2296 WS-7-1-2 5.265 12.1 198.5 35.46 3.059 2.227 8.476 0.2345 0.2501 WS-7-1-3 4.768 11.73 395.7 38.8 2.822 2.559 8.125 0.2763 0.2647 WS-7-2-1 4.653 14.38 224.9 39.73 3.334 2.718 9.864 0.3091 0.2362 WS-7-2-2 5.304 13.17 257.9 34.03 1.777 1.895 8.438 0.1523 0.1659 WS-7-2-3 5.435 18.1 301.3 39.84 4.916 3.444 9.351 0.3448 0.2486 WS-9-1-1 3.998 48.69 30.94 18.73 2.405 2.775 9.283 0.2899 0.2748 WS-9-1-2 4.099 26.59 103.1 27.1 1.968 1.822 9.577 0.1389 0.2715 WS-9-1-3.1 3.409 23.28 346.9 28.72 3.176 2.691 8.589 0.297 0.2877 WS-8-2 2.633 19.27 101.7 21.05 4.323 3.654 9.724 0.2029 0.2831 WS-8-2.2 0.6947 19.59 40.87 12.48 2.029 2.658 6.417 0.2072 0.2304 WS-8-4 0.6829 23.17 37.77 11.66 0.3279 0.4235 1.697 0.1171 0.0331 WS-8-8.1 5.981 21.95 90.27 13.08 3.861 0.4214 7.003 0.2564 0.0252 WS-16-1.1 9.434 39.85 142.9 26.79 32.56 17.6 9.336 1.867 0.5757 WS-16-1.3 0.9012 29.79 64.25 12.32 1.278 0.8579 6.472 0.1117 0.0967 WS-16-3.1 5.297 36.11 68.3 11.04 2364 1.398 10.97 53.93 0.1694 WS-16-4 3.725 27.07 54.13 10.39 13.51 14.59 8.72 1.044 0.7895 WS-61-2 2.66 68.48 49.7 12.08 75.99 0.22 11.72 4.096 0.037 WS-61-4 2.28 73.44 93.1 14.26 3.679 3.337 15.07 0.2873 0.4215 WS-61-7 7.793 71.04 51.21 11.71 11.42 10.06 9.692 0.5085 0.7796
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