Genesis of Yinan gold deposit in Luxi district: Constrain from REE and trace elements of sulfide ore and wall-rock
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摘要:
沂南金矿床为鲁西地区典型的矽卡岩型矿床，产于早白垩世中酸性杂岩与新太古界—寒武系接触带及其附近。本次利用岩/矿石稀土和微量元素组成，示踪成矿物质来源及成矿流体地球化学性质。结果显示，成矿的闪长玢岩负Eu异常不显著，且早矿化阶段发育大量磁铁矿，暗示早阶段成矿流体具有氧化性特征。晚(金)矿化阶段的黄铁矿和黄铜矿相对富集轻稀土元素和高场强元素，负Eu异常显著，Ce异常不明显，且Hf/Sm、Nb/La值大于1，显示含F−的还原性流体特征。矿石的Y/Ho、Zr/Hf和Nb/Ta值变化较大，且黄铁矿Co/Ni>10，表明成矿流体源于岩浆水和大气降水的混入。矿石与赋矿围岩具有相似的稀土元素配分模式和微量元素地球化学行为，且具有相同范围/趋势的微量元素比值，说明沂南杂岩体和碳酸盐岩提供了必要的成矿物质。综上，沂南金矿床的成矿过程得到了较好的约束，同时也对区域范围内金矿成因有一定指示意义。
Abstract:The Yinan gold deposit is a representative skarn deposit in the Luxi district, mainly produced in and around the contact zone between the Early Cretaceous intermediate−acid complex and the Neoarchean and Cambrian strata. The present work traces the source of ore−forming material and geochemical properties of ore−forming fluids by using rock/ore rare earth and trace element compositions. The ore−forming diorite porphyrite does not show a negative Eu anomaly, and a large amount of magnetite is developed in the early mineralized stage, suggesting that the ore−forming fluid in the early stage is oxidized. Pyrite and chalcopyrite in the late (gold) mineralization stage are relatively enriched in light rare earth elements and high field strength elements, with significant negative Eu anomaly and insignificant Ce anomaly, and Hf/Sm and Nb/La ratios greater than 1, showing the characteristics of F−bearing reductive fluids. The Y/Ho, Zr/Hf and Nb/Ta ratios in the ore are highly variable, and the Co/Ni in the pyrite is more than 10, indicating that the ore−forming fluid originated from the mixing of magmatic water and meteoric water. The ore and the ore−bearing wall rocks have similar rare earth elements partitioning patterns and trace elements geochemical behavior, with the same range/trend of trace element ratios, suggesting that the Yi’nan complex and carbonate rocks provide the necessary ore−forming material. In summary, the mineralization process of the Yi’nan gold deposit has been well constrained, and it also has certain indicative significance for the genesis of gold deposits within the region.
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图 1 华北板块地质简图(a, 据Zhao et al., 2005修改)和鲁西地区地质图及其矽卡岩型铁−金矿床分布(b, 据Deng et al., 2018修改)
Figure 1.
图 2 沂南金矿床金场(a)和铜井矿区(b)地质图(据胡芳芳等，2010，钱建平等，2017；Duan et al., 2020修改)
Figure 2.
图 5 沂南金矿床矿石(a, c)和赋矿围岩(b, d)球粒陨石标准化稀土元素配分模式图解(底图据Boynton, 1984)
Figure 5.
图 6 沂南金矿床矿石(a, c)和赋矿围岩(b，d)原始地幔标准化微量元素蛛网图解(底图据Sun et al., 1989)
Figure 6.
图 7 沂南金矿黄铁矿Ni−Co分布图(Deditius et al., 2013; Cioacă et al., 2014; Keith et al., 2016; Zhang et al., 2016)
Figure 7.
表 1 沂南金矿床矿石及赋矿围岩稀土和微量元素测试样品描述及采样位置
Table 1. Location and characteristics of samples for analysis of REE and trace elements in ores and host rocks in the Yinan gold deposit
序号 样品号 矿区名称 样品类型 采样位置 样品描述 测试矿物/岩石 1 21YNT03 铜井 金铜矿石 汞泉东矿段二中段 黄铁矿、磁铁矿等矿物与角岩呈条带状分布 黄铁矿 2 21YNT12 铜井 金铜矿石 金龙矿段九中段 黄铜矿呈浸染状分布 黄铜矿 3 21YNT15 铜井 金铜矿石 汞泉东矿段二中段 浸染状黄铁矿和黄铜矿矿石，其中黄铁矿晶形较好 黄铁矿 4 21YNT18 铜井 金铜矿石 金龙矿段九中段 黄铁矿−石英脉 黄铁矿 5 21YNT19 铜井 近矿岩体 汞泉东矿段二中段 闪长玢岩 闪长玢岩 6 21YNT20 铜井 赋矿岩体 汞泉东矿段二中段 蚀变闪长玢岩 闪长玢岩 7 21YNT21 铜井 近矿地层 金龙矿段九中段 大理岩 大理岩 8 21YNJ02 金场 金铜矿石 矿石堆 块状矿石(黄铁矿和黄铜矿) 黄铁矿/黄铜矿 9 21YNJ05 金场 金铜矿石 矿石堆 块状矿石(黄铜矿)，与少量石英共生 黄铜矿 10 21YNJ06 金场 赋矿岩石 矿石堆 条带状矽卡岩 矽卡岩 11 21YNJ10 金场 赋矿地层 矿石堆 蚀变灰岩 灰岩 
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表 2 沂南金矿床矿石及赋矿围岩稀土元素含量及特征值
Table 2. REE element abundances and features of ore and host rocks in the Yinan gold deposit
10−6 元素 铜井矿区 21YNT03-1 21YNT03-2 21YNT12-1 21YNT12-2 21YNT15-1 21YNT15-2 21YNT18-1 21YNT18-2 21YNT19-1 21YNT19-2 21YNT20 黄铁矿 黄铁矿 黄铜矿 黄铜矿 黄铁矿 黄铁矿 黄铁矿 黄铁矿 闪长玢岩 闪长玢岩 蚀变闪
长玢岩La 0.390 0.328 0.168 0.280 0.293 0.431 0.195 0.128 30.543 26.498 25.851 Ce 0.785 0.615 0.296 0.355 0.683 0.917 0.425 0.246 48.934 44.735 43.679 Pr 0.099 0.092 0.029 0.034 0.105 0.114 0.050 0.023 5.143 4.865 5.298 Nd 0.452 0.401 0.117 0.103 0.379 0.469 0.171 0.089 19.533 18.362 21.658 Sm 0.077 0.085 0.023 0.018 0.080 0.101 0.021 0.017 3.506 3.261 4.155 Eu 0.017 0.013 0.005 0.005 0.007 0.012 0.007 0.003 1.095 1.096 1.082 Gd 0.107 0.092 0.026 0.024 0.103 0.128 0.041 0.020 3.281 3.171 3.397 Tb 0.020 0.020 0.004 0.006 0.016 0.021 0.006 0.002 0.483 0.475 0.456 Dy 0.101 0.110 0.033 0.013 0.071 0.117 0.035 0.012 2.654 2.585 2.413 Ho 0.027 0.025 0.005 0.005 0.014 0.026 0.008 0.003 0.547 0.532 0.449 Er 0.071 0.078 0.021 0.012 0.047 0.073 0.030 0.014 1.500 1.499 1.207 Tm 0.016 0.010 0.003 0.002 0.006 0.010 0.003 0.001 0.230 0.225 0.178 Yb 0.106 0.093 0.022 0.014 0.047 0.085 0.022 0.013 1.560 1.505 1.079 Lu 0.012 0.010 0.002 0.001 0.008 0.008 0.003 0.001 0.241 0.222 0.150 Y 3.632 3.596 3.172 3.139 3.478 3.641 3.254 3.152 16.101 14.693 13.978 ΣREE 2.280 1.972 0.752 0.873 1.859 2.512 1.019 0.571 119.249 109.032 111.052 LREE 1.820 1.534 0.637 0.795 1.547 2.044 0.869 0.506 108.754 98.817 101.723 HREE 0.460 0.438 0.115 0.077 0.312 0.468 0.150 0.065 10.495 10.215 9.329 LREE/
HREE3.952 3.502 5.541 10.307 4.961 4.367 5.812 7.752 10.362 9.673 10.904 LaN/YbN 2.637 2.531 5.483 14.179 4.480 3.623 6.403 7.322 14.048 12.630 17.178 δEu 0.566 0.434 0.583 0.806 0.238 0.327 0.716 0.458 0.987 1.042 0.880 δCe 0.982 0.867 1.040 0.887 0.953 1.013 1.056 1.101 0.957 0.966 0.915 Gd/Lu 8.796 9.418 11.821 27.071 12.573 16.271 11.941 18.119 13.608 14.258 22.584 La/Sm 5.033 3.844 7.423 15.543 3.669 4.279 9.286 7.637 8.712 8.126 6.221 元素 铜井矿区 金场矿区 21YNT21-1 21YNT21-2 21YNJ02-1 21YNJ02-2 21YNJ02-3 21YNJ02-4 21YNJ05 21YNJ06-1 21YNJ06-2 21YNJ10-1 21YNJ10-2 大理岩 大理岩 黄铁矿 黄铁矿 黄铜矿 黄铜矿 黄铜矿 石榴子石
矽卡岩矽卡岩
化围岩蚀变灰岩 蚀变灰岩 La 3.164 3.006 0.202 0.230 0.135 0.137 0.269 45.158 2.734 2.259 2.016 Ce 5.791 5.104 0.457 0.481 0.200 0.208 0.388 63.569 13.887 3.701 3.381 Pr 0.822 0.753 0.072 0.075 0.026 0.024 0.083 6.437 3.557 0.495 0.478 Nd 3.328 2.931 0.316 0.371 0.076 0.108 0.406 21.335 18.114 1.879 1.818 Sm 0.676 0.616 0.115 0.114 0.010 0.024 0.128 3.986 3.758 0.327 0.317 Eu 0.152 0.129 0.013 0.015 0.003 0.003 0.015 0.743 1.118 0.061 0.059 Gd 0.725 0.658 0.163 0.143 0.029 0.035 0.190 3.680 3.106 0.300 0.306 Tb 0.117 0.113 0.034 0.033 0.004 0.006 0.037 0.624 0.466 0.043 0.044 Dy 0.707 0.715 0.211 0.225 0.018 0.035 0.214 3.599 2.484 0.204 0.263 Ho 0.159 0.144 0.043 0.052 0.004 0.009 0.053 0.788 0.524 0.044 0.049 Er 0.495 0.447 0.134 0.144 0.019 0.024 0.151 2.283 1.403 0.113 0.140 Tm 0.082 0.073 0.023 0.022 0.001 0.005 0.023 0.337 0.219 0.015 0.016 Yb 0.496 0.455 0.150 0.168 0.018 0.029 0.155 2.285 1.463 0.104 0.110 Lu 0.077 0.071 0.018 0.020 0.002 0.004 0.020 0.341 0.201 0.013 0.018 Y 7.078 6.729 3.873 3.873 3.140 3.217 3.825 19.476 15.547 4.559 4.658 ΣREE 16.792 15.215 1.952 2.091 0.546 0.651 2.131 155.165 53.036 9.558 9.014 LREE 13.933 12.539 1.175 1.284 0.450 0.504 1.288 141.228 43.169 8.722 8.068 HREE 2.858 2.677 0.777 0.807 0.096 0.147 0.843 13.937 9.867 0.836 0.946 LREE/
HREE4.875 4.684 1.512 1.592 4.693 3.418 1.527 10.133 4.375 10.436 8.525 LaN/YbN 4.576 4.738 0.965 0.983 5.264 3.351 1.243 14.177 1.341 15.615 13.105 δEu 0.662 0.618 0.283 0.352 0.529 0.282 0.300 0.593 1.000 0.594 0.577 δCe 0.881 0.832 0.930 0.898 0.828 0.889 0.640 0.914 1.092 0.858 0.845 Gd/Lu 9.381 9.295 8.842 7.149 12.768 7.733 9.564 10.800 15.426 23.236 17.078 La/Sm 4.677 4.876 1.761 2.019 13.837 5.716 2.102 11.329 0.728 6.898 6.364
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表 3 沂南金矿床矿石及赋矿围岩微量元素含量及特征值
Table 3. Trace element abundances and features of the ore and host rocks in the Yinan gold deposit
10−6 元素 铜井矿区 21YNT03-1 21YNT03-2 21YNT12-1 21YNT12-2 21YNT15-1 21YNT15-2 21YNT18-1 21YNT18-2 21YNT19-1 21YNT19-2 21YNT20 黄铁矿 黄铁矿 黄铜矿 黄铜矿 黄铁矿 黄铁矿 黄铁矿 黄铁矿 闪长玢岩 闪长玢岩 弱蚀变闪长玢岩 Cs 0.052 0.040 0.036 0.029 0.038 0.054 0.043 0.025 2.699 2.378 6.814 Rb 0.765 0.527 0.269 0.194 0.742 0.902 0.345 0.191 40.075 33.483 40.192 Ba 5.833 5.081 4.123 5.040 2.706 3.642 4.802 3.743 759.568 781.208 157.542 Th 0.265 0.484 0.170 0.095 0.119 0.256 0.167 0.101 3.324 3.218 3.258 U 0.134 0.136 0.052 0.056 0.200 0.400 0.045 0.053 1.204 1.107 1.373 Nb 8.638 13.925 0.518 1.612 3.034 0.487 2.468 1.903 6.299 6.546 8.452 Ta 3.859 4.381 0.412 0.519 0.928 0.303 1.655 1.006 1.126 0.945 3.136 La 0.390 0.328 0.168 0.280 0.293 0.431 0.195 0.128 30.543 26.498 25.851 Ce 0.785 0.615 0.296 0.355 0.683 0.917 0.425 0.246 48.934 44.735 43.679 Sr 4.400 4.100 3.900 4.800 5.271 5.344 3.382 3.718 517.660 484.070 434.540 Nd 0.452 0.402 0.117 0.103 0.379 0.469 0.171 0.089 19.533 18.362 21.658 P 19.290 16.560 4257.000 4136.000 60.090 63.600 19.780 30.030 758.900 757.500 783.900 Zr 23.845 20.143 11.954 12.705 12.670 14.707 12.462 11.930 265.360 242.770 294.750 Hf 0.407 0.381 0.091 0.167 0.097 0.185 0.126 0.093 5.909 5.737 5.912 Sm 0.077 0.085 0.023 0.018 0.080 0.101 0.021 0.017 3.506 3.261 4.155 Eu 0.017 0.013 0.005 0.006 0.007 0.012 0.007 0.003 1.095 1.096 1.082 Ti 274.700 303.800 120.700 251.400 106.800 131.600 104.900 87.880 3424.000 3411.000 3594.000 Gd 0.107 0.092 0.026 0.024 0.103 0.128 0.041 0.020 3.281 3.171 3.397 Tb 0.020 0.020 0.004 0.006 0.016 0.021 0.006 0.002 0.483 0.475 0.456 Y 3.632 3.596 3.172 3.139 3.479 3.641 3.254 3.152 16.101 14.693 13.978 Yb 0.106 0.093 0.022 0.014 0.047 0.085 0.022 0.013 1.560 1.505 1.080 Lu 0.012 0.010 0.002 0.001 0.008 0.008 0.004 0.001 0.241 0.222 0.150 Ho 0.027 0.025 0.005 0.005 0.014 0.026 0.008 0.003 0.547 0.532 0.449 Co 855.316 852.567 446.198 402.098 341.004 396.511 737.108 818.595 23.530 22.717 12.297 Ni 29.413 29.074 279.981 255.028 862.713 864.136 67.802 70.083 99.635 96.307 43.276 Hf/Sm 5.255 4.475 4.027 9.256 1.221 1.843 6.000 5.518 1.685 1.759 1.423 Th/La 0.680 1.477 1.011 0.341 0.408 0.595 0.856 0.786 0.109 0.121 0.126 Nb/La 22.167 42.519 3.091 5.759 10.363 1.131 12.669 14.832 0.206 0.247 0.327 Y/Ho 136.029 144.088 600.149 672.711 256.691 140.229 383.070 1040.937 29.447 27.593 31.155 Co/Ni 29.079 29.324 1.594 1.577 0.395 0.459 10.872 11.680 0.236 0.236 0.284 Nb/Ta 2.239 3.179 1.258 3.104 3.271 1.607 1.491 1.891 5.595 6.926 2.695 Zr/Hf 58.630 52.827 131.363 76.261 130.082 79.326 98.905 128.695 44.909 42.315 49.857 Th/U 1.973 3.550 3.235 1.713 0.597 0.641 3.696 1.890 2.761 2.907 2.373 La/Sm 5.035 3.844 7.416 15.544 3.669 4.279 9.276 7.637 8.712 8.126 6.221 Gd/Lu 8.810 9.408 11.773 26.667 12.573 16.228 11.829 17.727 13.608 14.258 22.588 (La/Sm)/
(Gd/Lu)0.572 0.409 0.630 0.583 0.292 0.264 0.784 0.431 0.640 0.570 0.275
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续表 3 元素 铜井矿区 金场矿区 大理岩 大理岩 黄铁矿 黄铁矿 黄铜矿 黄铜矿 黄铜矿 石榴子石 矽卡岩
化围岩蚀变灰岩 蚀变灰岩 21YNT21-1 21YNT21-2 21YNJ02-1 21YNJ02-2 21YNJ02-3 21YNJ02-4 21YNJ05 21YNJ06-1 21YNJ06-2 21YNJ10-1 21YNJ10-2 Cs 0.159 0.047 0.045 0.067 0.020 0.027 0.043 6.485 0.188 0.809 0.700 Rb 1.919 0.593 1.485 1.867 0.314 0.626 0.999 99.921 5.090 3.377 2.862 Ba 20.649 14.398 3.168 2.656 4.294 2.638 3.104 104.114 11.261 7.953 7.463 Th 0.258 0.208 0.281 0.331 0.071 0.141 0.187 13.819 2.236 0.303 0.392 U 0.160 0.120 3.822 3.890 0.228 0.989 3.224 13.442 5.685 0.590 0.896 Nb 7.665 7.113 0.578 0.449 0.551 5.168 3.152 37.001 12.746 0.923 18.766 Ta 2.782 1.736 0.387 0.474 0.561 2.329 1.799 4.849 2.052 0.340 5.246 La 3.164 3.006 0.202 0.230 0.135 0.137 0.269 45.158 2.734 2.259 2.016 Ce 5.792 5.104 0.457 0.481 0.200 0.208 0.388 63.569 13.887 3.701 3.381 Sr 196.080 176.800 3.564 3.553 3.269 3.242 3.743 312.007 21.879 94.896 91.400 Nd 3.328 2.931 0.316 0.371 0.076 0.108 0.406 21.335 18.114 1.879 1.818 P 60.570 23.980 30.520 50.230 4397.000 4346.000 4237.000 679.700 161.600 8.070 56.280 Zr 45.961 51.470 12.244 13.433 10.307 12.148 11.373 405.413 77.616 18.761 18.676 Hf 1.118 1.271 0.107 0.170 0.070 0.111 0.098 10.182 1.895 0.296 0.312 Sm 0.676 0.616 0.115 0.114 0.010 0.024 0.128 3.986 3.758 0.327 0.317 Eu 0.152 0.129 0.013 0.015 0.003 0.003 0.015 0.743 1.118 0.061 0.059 Ti 759.200 847.900 97.460 124.900 88.170 122.200 95.110 5746.000 1072.000 141.800 202.600 Gd 0.725 0.658 0.163 0.143 0.029 0.035 0.190 3.680 3.106 0.300 0.306 Tb 0.117 0.113 0.034 0.033 0.004 0.006 0.037 0.624 0.466 0.043 0.044 Y 7.078 6.729 3.873 3.873 3.140 3.217 3.825 19.476 15.547 4.559 4.658 Yb 0.496 0.455 0.150 0.168 0.018 0.029 0.155 2.285 1.463 0.104 0.110 Lu 0.077 0.071 0.018 0.020 0.002 0.004 0.020 0.341 0.201 0.013 0.018 Ho 0.159 0.144 0.043 0.052 0.004 0.009 0.053 0.788 0.524 0.044 0.049 Co 4.361 4.807 272.699 269.554 15.153 14.485 58.531 9.604 2.675 0.702 2.619 Ni 7.176 6.543 24.527 20.737 6.424 6.284 71.469 28.044 5.965 4.594 4.174 Hf/Sm 1.653 2.062 0.929 1.495 7.179 4.638 0.764 2.554 0.504 0.903 0.984 Th/La 0.081 0.069 1.386 1.443 0.526 1.028 0.698 0.306 0.818 0.134 0.195 Nb/La 2.423 2.366 2.857 1.957 4.069 37.637 11.737 0.819 4.661 0.409 9.310 Y/Ho 44.424 46.652 89.374 75.208 827.246 342.018 71.906 24.720 29.646 102.442 95.387 Co/Ni 0.608 0.735 11.118 12.999 2.359 2.305 0.819 0.342 0.449 0.153 0.627 Nb/Ta 2.756 4.096 1.496 0.949 0.983 2.219 1.753 7.630 6.212 2.713 3.577 Zr/Hf 41.106 40.496 114.604 79.013 146.612 109.028 116.489 39.817 40.964 63.426 59.898 Th/U 1.610 1.738 0.073 0.085 0.313 0.143 0.058 1.028 0.393 0.514 0.438 La/Sm 4.677 4.876 1.761 2.019 13.837 5.716 2.102 11.329 0.728 6.898 6.364 Gd/Lu 9.382 9.291 8.842 7.149 12.768 7.733 9.564 10.800 15.426 23.236 17.078 (La/Sm)/(Gd/Lu) 0.499 0.525 0.199 0.282 1.084 0.739 0.220 1.049 0.047 0.297 0.373
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