Trace Element Geochemical Characteristics of Gold−Bearing Pyrite from the Shijia Gold Deposit in Penglai, Shandong Province and Its Constraints on Ore−Forming Fluids
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摘要:
石家金矿床是位于胶东蓬莱−栖霞成矿带北段的一个石英脉型金矿床，其成矿过程大致可以分为石英−黄铁矿−绢云母阶段（Ⅰ）、石英−多金属硫化物−金阶段（Ⅱ）和石英−方解石−萤石阶段（Ⅲ）。为探讨石家金矿床成矿流体的性质，采用电感耦合等离子质谱仪（ICP−MS）技术，对石英−多金属硫化物−金阶段与自然金共生的黄铁矿开展微量元素分析。结果表明，黄铁矿富集Cu、Pb、Zn等亲硫元素，并且主要以矿物包裹体的形式赋存于黄铁矿中。稀土元素总量较低（ΣREE值为2.55×10−6～20.94×10−6），呈现出轻稀土元素富集、重稀土元素亏损的配分模式，LREE/HREE与(La/Yb)N值分别为16.15～52.12和18.26～481.62。黄铁矿表现出显著的Eu负异常（δEu值为0.16～0.62）而无明显Ce异常（δCe值为0.89～1.33），Hf/Sm、Th/La、Nb/La值均小于1。结合前人流体包裹体的研究，认为黄铁矿是在流体不混溶的作用下，从富Cl的还原性流体中沉淀的。Y/Ho、Zr/Hf、Nb/Ta值变化范围大，暗示成矿过程中热液体系受到了干扰，可能有大气降水的加入。Co、Ni含量和Co/Ni值显示黄铁矿为热液成因，成矿流体具有变质热液的特点，可能与富集岩石圈地幔的去挥发分作用有关。
Abstract:The Shijia gold deposit is a quartz−vein type gold deposit located in the north of the Penglai−Qixia gold belt in Jiaodong. The mineralization process of Shijia can be roughly divided into quartz−pyrite−sericite (I), quartz−polymetallic sulfide−gold (II) and quartz−calcite−fluorite (III) stages. The rare earth element (REE) and trace elements of pyrite coexisting with natural gold in the quartz−polymetallic sulfide−gold stage was analyzed by inductively coupled plasma mass spectrometry (ICP−MS) to discuss the properties of ore−forming fluids in the Shijia gold deposit. Results show that pyrite is relatively enriched in sulphophile elements such as Cu, Pb, Zn, and mainly occurs in pyrite in the form of mineral inclusions. The contents of REE in pyrite are relatively low, enriched in LREE, and depleted in HREE, with ΣREE, LREE/HREE values and (La/Yb)N values of 2.55×10−6～20.94×10−6, 16.15～52.12 and of 18.26～481.62, respectively. Pyrite shows significant negative Eu anomalies (δEu=0.16～0.62) but no obvious Ce anomalies (δCe=0.89～1.33), and Hf/Sm, Th/La, Na/La ratios are all less than 1. Combined with previous studies of fluid inclusions, it is indicating that pyrite is precipitated from a reducing fluid dominated by Cl−enriched under the mechanism of fluid immiscibility. The wide variation range of Y/Ho, Zr/Hf, and Nb/Ta ratios suggests that the hydrothermal system was disturbed during the mineralization process, which may be related to the addition of meteoric water. The contents of Co and Ni and the Co/Ni values indicate that the pyrite is of hydrothermal origin, and the ore−forming fluids are presumed to be similar to the metamorphic fluid which may be associated with the devolatilization of the enriched lithospheric mantle.
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Key words:
- pyrite /
- rare−earth elements /
- trace elements /
- ore−forming fluids /
- Shijia gold deposit /
- Jiaodong
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图 1 胶东半岛大地构造位置图（a）（据Zhao et al.，2005修改）、胶东金矿集区金矿床分布图（b）（据Deng et al.，2020修改）、 大柳行地区地质简图（c）（据Feng et al.，2020修改）
Figure 1.
图 6 石家金矿床主成矿阶段黄铁矿稀土元素配分曲线（球粒陨石REE数据据Sun et al.，1989）
Figure 6.
表 1 石家金矿床主成矿阶段黄铁矿微量元素分析品采样位置统计表
Table 1. Location of trace element analysis sample of ore–main stage pyrite from the Shijia gold deposit
序号 样品编号 矿体编号 勘探线编号 采样深度（m） 样品类型 1 SJ-1Py 326 28线 −595 含黄铁矿石英脉 2 SJ-2Py 326 28线 −555 含黄铁矿石英脉 3 SJ-3Py 326 28线 −515 含黄铁矿石英脉 4 SJ-4Py 326 28线 −475 含黄铁矿石英脉 5 SJ-5Py 326 28线 −435 含黄铁矿石英脉 6 SJ-6Py 326 28线 −395 多金属硫化物石英脉 7 SJ-7Py 326 28线 −355 乳白色石英–多金属硫化物脉 8 SJ-8Py 326 32线 −315 乳白色石英–多金属硫化物脉 9 SJ-9Py 326 40线 −280 乳白色石英–多金属硫化物脉 10 SJ-10Py 326 40线 −240 乳白色石英硫化物脉 11 SJ-11Py 326 52～56线 −205 乳白色石英硫化物脉 12 SJ-12Py 326 56线 −165 乳白色石英硫化物脉 13 SJ-13Py M2 12线 −745 石英硫化物脉 14 SJ-14Py M2 4线 −635 石英硫化物脉 15 SJ-15Py M2 4线 −595 含黄铁矿石英脉 16 SJ-16Py M2 4线 −555 石英硫化物脉 
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表 2 石家金矿床主成矿阶段黄铁矿稀土元素含量（10−6）及其特征值统计表
Table 2. REE content (10−6) and characteristic values of the ore–main stage pyrite from the Shijia gold deposit
样品
编号La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ΣREE LREE/HREE （La/Yb）N δEu δCe SJ-1Py 1.09 2.11 0.23 0.84 0.11 0.005 0.087 0.003 0.029 – 0.004 0.003 0.005 – 4.51 33.42 156.37 0.16 1.04 SJ-2Py 1.73 2.95 0.29 1.09 0.14 0.019 0.102 0.006 0.018 – 0.011 0.002 0.005 – 6.36 43.19 248.19 0.48 1.02 SJ-3Py 4.7 10.1 0.99 3.56 0.28 0.04 0.285 0.017 0.082 – 0.039 0.003 0.007 – 20.11 45.44 481.62 0.43 1.15 SJ-4Py 1.03 1.91 0.21 0.73 0.08 0.004 0.052 – 0.015 – 0.005 0.002 0.002 – 4.04 52.12 369.41 0.19 1.01 SJ-5Py 1.55 2.41 0.28 1.04 0.1 0.006 0.096 – 0.039 – 0.005 0.006 0.02 – 5.56 32.49 55.59 0.18 0.89 SJ-6Py 1.64 4.33 0.39 1.47 0.13 0.017 0.127 0.008 0.043 – 0.015 0.003 0.014 – 8.19 37.98 84.03 0.4 1.33 SJ-7Py 3.38 6.75 0.77 3.09 0.44 0.028 0.32 0.027 0.092 – 0.027 0.003 0.014 – 14.93 29.92 173.18 0.23 1.03 SJ-8Py 4.11 7.57 0.85 3.24 0.48 0.04 0.342 0.035 0.143 0.005 0.042 0.006 0.05 0.003 16.92 26.02 58.96 0.3 0.99 SJ-9Py 0.64 1.19 0.12 0.45 0.07 0.003 0.045 – 0.014 – 0.007 0.003 0.011 – 2.55 30.9 41.73 0.17 1.05 SJ-10Py 0.56 1.09 0.12 0.54 0.09 0.012 0.067 0.003 0.043 – 0.009 0.005 0.022 – 2.56 16.15 18.26 0.48 1.03 SJ-11Py 4.32 7.34 0.81 3.2 0.49 0.057 0.367 0.033 0.159 0.014 0.061 0.01 0.054 0.006 16.92 23.03 57.38 0.41 0.96 SJ-12Py 1.05 2.21 0.26 1.07 0.18 0.013 0.106 0.01 0.056 – 0.02 0.003 0.014 0.003 4.99 22.54 53.8 0.29 1.05 SJ-13Py 15.5 26.7 3.06 11.7 1.74 0.291 1.17 0.122 0.46 0.032 0.117 0.019 0.06 0.017 60.99 29.54 185.30 0.62 0.95 SJ-14Py 1.37 2.45 0.268 1.04 0.162 0.01 0.117 0.012 0.046 0.004 0.032 0.008 0.03 0.005 5.55 20.87 32.76 0.22 0.99 SJ-15Py 4.72 9.1 1.11 4.4 0.766 0.089 0.485 0.05 0.171 0.003 0.028 0.004 0.017 – 20.94 26.63 199.16 0.45 0.97 SJ-16Py 1.07 1.86 0.196 0.74 0.081 0.01 0.068 – 0.014 – – 0.003 0.004 – 4.05 44.46 191.88 0.41 1.00 注：–表示低于检测限。
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表 3 石家金矿床主成矿阶段黄铁矿微量元素含量（10−6）及其特征值统计表
Table 3. Trace elements content (10−6) and characteristic values of the ore−main stage pyrite from the Shijia gold deposit
样品
编号SJ-
1PySJ-
2PySJ-
3PySJ-
4PySJ-
5PySJ-
6PySJ-
7PySJ-
8PySJ-
9PySJ-
10PySJ-
11PySJ-
12PySJ-
13PySJ-
14PySJ-
15PySJ-
16PyLi 0.32 0.278 0.319 0.319 0.537 0.801 0.386 0.291 0.325 0.396 0.854 0.242 0.55 0.185 0.33 0.268 Be 0.004 0.011 0.009 − 0.002 0.014 − 0.033 0.008 0.006 0.024 0.004 0.022 0.003 0.003 0.005 Sc 0.275 0.23 0.252 0.371 0.036 0.293 0.374 0.495 0.435 0.268 0.39 0.28 0.429 0.275 0.229 0.29 V 0.263 0.197 0.303 0.256 0.453 0.37 0.26 0.745 0.479 0.329 1.29 0.28 0.429 0.442 0.217 0.239 Cr 0.726 − 1.92 1.89 0.745 0.008 2.25 3.47 1.06 0.215 2.16 0.08 1.55 1.07 − − Co 88.2 46.8 19.6 4.72 3.01 1.45 9.97 110 30.8 45.9 41.7 53.9 209 196 295 46.4 Ni 88.7 43.9 11.9 5.55 2.96 2.75 8.33 88.8 11.3 10.8 74.8 34.5 50.1 193 629 43.7 Cu 157 133 186 231 293 198 179 27.9 125 147 263 67.8 21.5 85.6 184 131 Zn 858 419 5316 3292 ＞10000 3426 8811 185 576 1871 1979 1230 51.4 632 1245 425 Ga 0.447 0.398 0.913 0.914 1.2 1.1 0.917 0.562 0.405 0.657 0.673 0.403 0.425 1.36 0.38 0.408 Rb 0.416 0.299 0.421 0.351 0.585 0.447 0.521 2.42 0.787 0.737 1.43 0.394 0.804 0.472 0.272 0.31 Sr 3.24 1.01 4.05 2.14 4.34 4.55 3.05 3.35 2.95 5.06 4.31 1.27 0.871 1.01 1.15 1.04 Y 0.069 0.074 0.135 0.584 0.116 0.203 0.191 0.403 0.085 0.217 0.425 0.153 0.719 0.194 0.252 0.055 Mo 0.013 0.294 0.158 0.006 0.028 − − 0.048 0.229 0.59 0.43 0.502 0.083 0.055 0.832 0.276 Cd 5.63 3.59 30.5 20.3 63.7 19.9 45.2 1.01 3.79 13.7 11.2 6 0.22 3.93 6.1 3.49 In 0.844 6.2 2.23 1.92 2.04 0.467 0.155 0.039 0.173 0.176 0.057 0.021 0.008 0.247 0.216 6.11 Sb 4.14 2.04 6.75 10.9 14.9 19.5 8.52 4.26 6.93 10.4 76.8 6.75 3.74 32.8 6.44 2.06 Cs 0.009 0.007 0.005 0.007 0.008 0.017 0.007 0.046 0.011 0.015 0.026 0.007 0.025 0.009 0.006 0.002 Ba 1.33 1.05 2.19 1.39 1.99 1.35 1.74 6.75 2.48 2.93 6.25 2.16 1.87 1.72 1.84 1.32 La 1.09 1.73 4.7 1.03 1.55 1.64 3.38 4.11 0.644 0.558 4.32 1.05 15.5 1.37 4.72 1.07 Sm 0.107 0.143 0.284 0.081 0.103 0.13 0.436 0.481 0.065 0.089 0.492 0.18 1.74 0.162 0.766 0.081 Ho − − − − − − − 0.005 − − 0.014 − 0.032 0.004 0.003 − W 0.007 0.026 0.018 0.005 − − − 0.044 0.009 0.017 0.128 − 0.026 0.072 0.008 0.024 Pb 616 268 4661 6342 9802 5189 4136 298 3511 7095 >10000 2647 117 4737 947 265 Bi 1.67 16.7 1.43 0.892 0.174 − − 4.68 0.199 0.489 0.309 0.253 2.95 1.19 2.64 16 Th 0.039 0.131 0.122 0.009 0.057 0.057 0.132 1.54 0.243 0.046 1.17 0.667 0.517 1.06 0.083 0.068 U 0.014 0.105 0.033 0.015 0.01 0.04 0.056 0.306 0.056 0.076 0.125 0.539 0.07 0.394 0.044 0.025 Nb 0.009 0.024 0.029 0.02 0.023 0.022 0.018 0.447 0.024 0.009 0.086 0.013 0.015 0.062 0.003 0.011 Ta 0.003 0.004 0.004 − 0.005 0.006 0.003 0.02 0.005 0.006 0.007 0.005 0.005 0.013 0.002 0.004 Zr 0.368 0.4 0.406 0.374 0.407 0.335 0.488 1.89 0.581 0.443 1.33 1.4 0.513 1.69 0.356 0.359 Hf 0.008 0.01 0.022 0.008 0.012 0.018 0.021 0.117 0.017 0.016 0.056 0.086 0.022 0.054 0.018 0.012 Sn 3.76 11.6 11.8 20.8 7.49 8.06 10.5 0.541 2.73 3.22 1.32 0.613 0.17 2.81 0.53 11.4 Co/Ni 0.99 1.07 1.65 0.85 1.02 0.53 1.20 1.24 2.73 4.25 0.56 1.56 4.17 1.02 0.47 1.06 Hf/Sm 0.07 0.07 0.08 0.10 0.12 0.14 0.05 0.24 0.26 0.18 0.11 0.48 0.01 0.33 0.02 0.15 Nb/La 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.11 0.04 0.02 0.02 0.01 0.00 0.05 0.00 0.01 Th/La 0.04 0.08 0.03 0.01 0.04 0.03 0.04 0.37 0.38 0.08 0.27 0.64 0.03 0.77 0.02 0.06 Y/Ho − − − − − − − 80.60 − − 30.36 − 22.47 48.50 84.00 − Zr/Hf 46.00 40.00 18.45 46.75 33.92 18.61 23.24 16.15 34.18 27.69 23.75 16.28 23.32 31.30 19.78 29.92 Nb/Ta 3.00 6.00 7.25 − 4.60 3.67 6.00 22.35 4.80 1.50 12.29 2.60 3.00 4.77 1.50 2.75 注：−表示低于检测限。
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